Piezoelectric polymer material and method for producing same

ABSTRACT

The invention provides a piezoelectric polymer material comprising a helical chiral polymer having a weight average molecular weight of from 50,000 to 1,000,000 and optical activity, the piezoelectric polymer material having: crystallinity as obtained by a DSC method of from 20% to 80%; a transmission haze with respect to visible light of 50% or less; and a product of the crystallinity and a standardized molecular orientation MORc, which is measured with a microwave transmission-type molecular orientation meter at a reference thickness of 50 μm, of from 40 to 700.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of PCT internationalapplication No. PCT/JP2011/069061 filed Aug. 24, 2011, which claimspriority under 35 USC 119 from Japanese Patent Application No.2010-188924 filed Aug. 25, 2010, Japanese Patent Application No.2010-203671 filed Sep. 10, 2010, and Japanese Patent Application No.2011-092349 filed Apr. 18, 2011, the disclosures of which areincorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to a piezoelectric polymer material and amethod for producing the piezoelectric polymer material.

2. Related Art

As piezoelectric materials, conventionally, PZT (PBZrO₃—PbTiO₃-basedsolid solution), which is a ceramic material, has often been used.However, since PZT contains lead, piezoelectric polymer materials, whichare more environmentally friendly and highly flexible, have beenincreasingly used.

The currently known piezoelectric polymer materials are generallyclassified into the following two types, i.e., poled polymers includingnylon 11, polyvinyl fluoride, polyvinyl chloride, polyurea and the like,and ferroelectric polymers including polyvinylidene fluoride (β-type)(PVDF), vinylidene fluoride-trifluoroethylene copolymer (P (VDF-TrFE))(75/25) and the like.

However, since piezoelectric polymer materials are inferior to PZT interms of piezoelectricity, there is demand for improvement inpiezoelectricity of piezoelectric polymer materials. Therefore, attemptshave been made from various viewpoints in order to improvepiezoelectricity of the piezoelectric polymer materials.

For example, PVDF and P(VDF-TrFE), which are ferroelectric polymers,exhibit excellent piezoelectricity among polymers and have apiezoelectric constant d₃₁ of 20 pC/N or more. In order to impartpiezoelectricity to film materials formed from PVDF or P(VDF-TrFE),polymer chains are oriented in a stretching direction by performingstretching and opposite charges are applied to both sides of the film bycorona discharge or the like, whereby an electric field is generated ina direction perpendicular to the film surface and permanent dipoles,containing fluorine in side chains of the polymer chains, are orientedin a direction parallel to the electric field direction.

However, there have been problems from practical viewpoints in thatopposite charges, such as water and ions in air, easily attach to thepolarized film surface in a direction of canceling the orientation and,as a result, orientation of the permanent dipoles that have beenarranged by the poling treatment is loosened, thereby causing asignificant decrease in piezoelectricity with time.

PVDF is a material that exhibits the highest piezoelectricity among thepiezoelectric polymer materials. However, since it has a comparativelyhigh dielectric constant, which is 13, among piezoelectric polymermaterials, the value of a piezoelectric g constant (open circuit voltageper unit stress), which is a value obtained by dividing a piezoelectricd constant by the dielectric constant, is small. In addition, althoughPVDF exhibits a favorable conversion efficiency from electricity tosound, its conversion efficiency from sound to electricity is yet to beimproved.

In recent years, polymers having optical activity, such as polypeptidesand polylactic acids, have gathered attention in addition to thepiezoelectric polymer materials as described above. Polylacticacid-based polymers are known to exhibit piezoelectricity by simplyperforming mechanical stretching.

Among polymers having optical activity, piezoelectricity of polymercrystals, such as polylactic acid, results from permanent dipoles withC═O bonds that are present in a helical axis direction. In particular,polylactic acid is an ideal polymer among polymers having helicalchirality due to its low volume fraction of side chains with respect toa main chain, and its large proportion of permanent dipoles per volume.

It is known that the polylactic acid, which exhibits piezoelectricity bysimply performing stretching, does not require a poling treatment andits piezoelectric modulus does not decrease over the years.

Since polylactic acids exhibit various piezoelectric properties asdescribed above, piezoelectric polymer materials produced from varioustypes of polylactic acids have been reported.

For example, a piezoelectric polymer material that exhibits apiezoelectric modulus of approximately 10 pC/N at room temperature,which is produced by stretching a molded product of polylactic acid, hasbeen disclosed (e.g., see Japanese Patent Application Laid-Open No.5-152638).

It has also been reported that a high piezoelectricity of approximately18 pC/N can be achieved by carrying out a special orientation method,which is referred to as forging, in order to make polylactic acidcrystals highly oriented (e.g., see Japanese Patent ApplicationLaid-Open No. 2005-213376).

However, both piezoelectric materials shown in Japanese PatentApplication Laid-Open No. 5-152638 and Japanese Patent ApplicationLaid-Open No. 2005-213376 are insufficient in transparency.

SUMMARY OF THE INVENTION

A first aspect of the invention provides a piezoelectric polymermaterial comprising a helical chiral polymer having a weight averagemolecular weight of from 50,000 to 1,000,000 and optical activity, thepiezoelectric polymer material having:

crystallinity as obtained by a DSC method of from 20% to 80%;

a transmission haze with respect to visible light of 50% or less; and

a product of the crystallinity and a standardized molecular orientationMORc, which is measured with a microwave transmission-type molecularorientation meter at a reference thickness of 50 μm, of from 40 to 700.

A second aspect of the invention provides a piezoelectric polymermaterial comprising a polylactic acid-based polymer and polyvinylidenefluoride, wherein a content of the polyvinylidene fluoride is from morethan 0 mass % to 5 mass % with respect to the total mass of thepolylactic acid-based polymer, and wherein a piezoelectric constant d₁₄measured by a resonance method at 25° C. is 10 pC/N or more.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view illustrating the constitution of a heat presstreatment used in the Examples in accordance with the first embodimentof the present invention.

FIG. 2 is a schematic view illustrating the constitution of a heat pressmachine used in the Examples in accordance with the first embodiment ofthe present invention.

DETAILED DESCRIPTION OF THE INVENTION

According to the first embodiment of the present invention, it ispossible to provide a piezoelectric polymer material that exhibits ahigh piezoelectric constant d₁₄ and excellent transparency anddimensional stability, and a method for producing the piezoelectricpolymer material.

According to the second embodiment of the present invention, it ispossible to provide a piezoelectric polymer material that exhibits ahigh piezoelectric constant d₁₄ and excellent transparency, and a methodfor producing the piezoelectric polymer material.

<Piezoelectric Polymer Material in Accordance with First Embodiment>

The piezoelectric polymer material in accordance with the firstembodiment includes a helical chiral polymer having a weight averagemolecular weight of from 50,000 to 1,000,000 and optical activity, thepiezoelectric polymer material having:

crystallinity as obtained by a DSC method of from 20% to 80%;

a transmission haze with respect to visible light of 50% or less; and

a product of the crystallinity and a standardized molecular orientationMORe, which is measured with a microwave transmission-type molecularorientation meter at a reference thickness of 50 μm, of from 40 to 700.

By having the constitution as set forth above, a piezoelectric polymermaterial that exhibits a high piezoelectric constant d₁₄ and excellenttransparency and dimensional stability can be obtained.

In the present specification, “piezoelectric constant d₁₄” refers to akind of tensor of piezoelectric modulus, and in a case in whichpolarization occurs in a direction of shear stress upon application of ashear stress to a stretched material in a direction of stretching axis,the density of charges generated per unit shear stress is defined asd₁₄. The greater the value of piezoelectric constant d₁₄ is, the higherthe piezoelectricity is.

In the present embodiment, the term “piezoelectric constant” refers to“piezoelectric constant d₁₄”.

The piezoelectric constant d₁₄ is a value calculated by a method asdescribed below. Specifically, a rectangular film whose longer side isat an angle of 45° with respect to a stretching direction is used as atest piece. Electrode layers are formed on the entire surface of frontand back sides of a principal plane of the test piece, respectively. Theamount of deformation of the film in the longer direction, which occursupon application of a voltage E (V) to the electrodes, is defined as X.The value of d₁₄ is defined as 2×deformation X/electric field intensityE (V/m), in which the value obtained by dividing the applied voltage E(V) by a film thickness t (m) is given as an electric field intensity E(V/m) and the amount of deformation in the longitudinal direction of thefilm upon application of E (V) is given as X.

In addition, a complex piezoelectric modulus d₁₄ is calculated asd₁₄=d₁₄′−id₁₄”, and d₁₄′ and id₁₄″ are obtained by RHEOLOGRAPH SOLIDS-1, manufactured by Toyo Seiki Seisaku-sho, Ltd. d₁₄′ represents thereal part of the complex piezoelectric modulus, id₁₄” represents theimaginary part of the complex piezoelectric modulus, and d₁₄′ (real partof the complex piezoelectric modulus) is equivalent to the piezoelectricconstant d₁₄ in accordance with the present embodiment.

The greater the real part of the complex piezoelectric modulus is, themore favorable the piezoelectricity is.

There is a piezoelectric constant d₁₄ as measured by a displacementmethod (unit: pm/V) and a piezoelectric constant d₁₄ as measured by aresonance method (unit: pC/N).

In one aspect of the present embodiment, the piezoelectric constant d₁₄as measured by a resonance method may be less than 10 pC/N.

[Helical Chiral Polymer Having Optical Activity]

The helical chiral polymer having optical activity refers to a polymerhaving a helical molecular structure and having molecular opticalactivity.

Helical chiral polymers having optical activity (hereinafter, alsoreferred to as “optically active polymers”) include, for example,polypeptides, cellulose derivatives, polylactic acid-based resins,polypropylene oxides, poly(β-hydroxybutyrate), and the like.

The polypeptides include, for example, poly(γ-benzyl glutarate),poly(γ-methyl glutarate), and the like.

The cellulose derivatives include, for example, cellulose acetate,cyanoethyl cellulose, and the like.

The optically active polymer preferably has an optical purity of 95.00%ee or more, more preferably 99.00% ee or more, and further preferably99.99% ee or more, from the viewpoint of improving piezoelectricity of apiezoelectric polymer material. The optical purity is desirably 100.00%ee. When the optical purity of an optically active polymer is within theabove-described range, it is considered that packing characteristics ofpolymer crystals that exhibit piezoelectricity is enhanced, therebyincreasing piezoelectricity of the optically active polymer.

In the present embodiment, the optical purity of the optically activepolymer is a value calculated by the following expression:

Optical purity(% ee)=100×|L-isomer amount−D-isomer amount|/(L-isomeramount+D-isomer amount)

In other words, a value obtained by multiplying the value obtained bydividing the difference (absolute value) between the amount [mass %] ofL-isomer of optically active polymer and the amount [mass %] of D-isomerof optically active polymer by the total of the amount [mass %] ofL-isomer of optically active polymer and the amount [mass %] of D-isomerof optically active polymer by 100 is referred to as optical purity.

The amount [mass %] of L-isomer of the optically active polymer and theamount [mass %] of D-isomer of the optically active polymer are obtainedby high precision liquid chromatography (HPLC). Details of themeasurement are described later.

Among the optically active polymers as described above, a compoundhaving a main chain that contains a repeating unit represented by thefollowing Formula (1) is preferred from the viewpoint of increasingoptical purity and improving piezoelectricity.

Exemplary compounds containing the repeating unit as a main chainrepresented by the Formula (1) include polylactic acid-based resins. Inparticular, polylactic acid is preferred, and a homopolymer of L-lacticacid (PLLA) or D-lactic acid (PDLA) is most preferred.

The polylactic acid-based resin refers to “polylactic acid,” “copolymerof L- or D-lactic acid with a copolymerizable polyfunctional compound”or a mixture thereof.

The “polylactic acid” is a polymer in which lactic acids are polymerizedvia ester bonds to form a long structure, and it is known thatpolylactic acid can be produced by a lactide method in which a lactideis formed as an intermediate, a direct polymerization method in whichlactic acid is heated in a solvent under reduced pressure to causepolymerization while removing water, or the like. Examples of polylacticacid include a homopolymer of L-lactic acid, a homopolymer of D-lacticacid, a block copolymer containing a polymers of at least one ofL-lactic acid or D-lactic acid, and a graft copolymer containing apolymer of at least one of L-lactic acid or D-lactic acid.

Examples of the copolymerizable polyfunctional compound as describedabove include hydroxycarboxylic acids such as glycolic acid, dimethylglycolate, 3-hydroxybutyrate, 4-hydroxybutyrate, 2-hydroxypropanoate,3-hydroxypropanoate, 2-hydroxyvalerate, 3-hydroxyvalerate,4-hydroxyvalerate, 5-hydroxyvalerate, 2-hydroxycaproate,3-hydroxycaproate, 4-hydroxycaproate, 5-hydroxycaproate,6-hydroxycaproate, 6-hydroxymethylcaproate and mandelic acid; cyclicesters such as glycolide, β-methyl-δ-valerolactone, γ-valerolactone and∈-caprolactone; polycarboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid,sebacic acid, undecanedioic acid, dodecanedioic acid and terephthalicacid; anhydrides of these compounds; polyhydric alcohols such asethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol,3-methyl-1,5-pentanediol, neopentyl glycol, tetramethylene glycol and1,4-hexanedimethanol; polysaccharides such as cellulose; aminocarboxylicacids such as α-amino acid; and the like.

Examples of the copolymer of lactic acid with a copolymerizablepolyfunctional compound include a block or graft copolymer having apolylactic acid sequence that can generate helical crystals.

The polylactic acid-based resin can be produced, for example, by amethod in which the resin is obtained by directly carrying outdehydrocondensation of lactic acid, as described in Japanese PatentApplication Laid-Open No. 59-096123 and Japanese Patent ApplicationLaid-Open No. 7-033861, a method in which a lactide, which is a cyclicdimer of lactic acid, is subjected to ring-opening polymerization, asdescribed in U.S. Pat. Nos. 2,668,182 and 4,057,357, and the like.

In order that the optically active polymer obtained by a method asdescribed above may have an optical purity of 95.00% ee or more, forexample, when the polylactic acid is produced by a lactide method, it ispreferable to use a lactide having an optical purity that has beenincreased to 95.00% ee or more by a crystallization operation forpolymerization.

[Weight Average Molecular Weight of Optically Active Polymer]

The optically active polymer in accordance with the present embodimentmay have a weight average molecular weight (Mw) of from 50,000 to1,000,000.

If the lower limit of the weight average molecular weight of theoptically active polymer is less than 50,000, mechanical strength of amolded product formed from the optically active polymer may beinsufficient. The lower limit of the weight average molecular weight ofthe optically active polymer is preferably 100,000 or more, furtherpreferably 200,000 or more. On the other hand, if the upper limit of theweight average molecular weight of the optically active polymer is morethan 1,000,000, it may be difficult to form a molded product such as afilm from the optically active polymer by carrying out extrusion or thelike. The upper limit of the weight average molecular weight ispreferably 800,000 or less, further preferably 300,000 or less.

The molecular weight distribution (Mw/Mn) of the optically activepolymer is preferably from 1.1 to 5, more preferably from 1.2 to 4, fromthe viewpoint of the strength of the piezoelectric polymer material. Themolecular weight distribution is further preferably from 1.4 to 3.

The weight average molecular weight Mw and the molecular weightdistribution (Mw/Mn) of a polylactic acid-based polymer can be measuredby a GPC measuring method as described below using a gel permeationchromatograph (GPC).

—GPC Measuring Apparatus—

GPC-100 manufactured by Waters Corporation

—Column—

SHODEX LF-804 manufactured by Showa Denko K.K.

—Preparation of Sample—

A polylactic acid-based polymer is dissolved in a solvent (e.g.,chloroform) at 40° C. to prepare a sample solution with a concentrationof 1 mg/ml.

—Measurement Conditions—

Into the column, 0.1 ml of the sample solution in the solvent(chloroform) is introduced at a temperature of 40° C. and a flow rate of1 ml/min.

The concentration of the sample in the sample solution separated in thecolumn is measured by a differential refractometer. A universalcalibration curve is produced with a polystyrene standard sample,thereby calculating the weight average molecular weight (Mw) and themolecular weight distribution (Mw/Mn) of the polylactic acid-basedpolymer.

The polylactic acid-based polymer may be a commercially availablepolylactic acid, and examples thereof include PURASORB (PD, PL)manufactured by PURAC Corporation, LACEA (H-100, H-400) manufactured byMitsui Chemicals Inc., and the like.

When a polylactic acid-based resin is used as the optically activepolymer, in order to produce a polylactic acid-based resin having aweight average molecular weight (Mw) of 50,000 or more, it is preferableto produce the optically active polymer by a lactide method or a directpolymerization method.

[Polyvinylidene Fluoride]

The piezoelectric polymer material in accordance with the presentembodiment may contain polyvinylidene fluoride at a rate of more than 0mass % and 5 mass % or less with respect to the total mass of thepolylactic acid-based polymer.

By including polyvinylidene fluoride together with the polylacticacid-based polymer, a piezoelectric polymer material having a highpiezoelectric constant and excellent transparency can be obtained. It isconsidered that polyvinylidene fluoride functions as a crystalnucleating agent.

The weight average molecular weight (Mw) of the polyvinylidene fluorideis preferably from 3,000 to 1,000,000.

The mechanical strength of the piezoelectric polymer material isexcellent when the lower limit of the weight average molecular weight is3,000 or more, while it is easy to perform molding (such as extrusion)of the piezoelectric polymer material when the upper limit of the weightaverage molecular weight is 1,000,000 or less. The lower limit of theweight average molecular weight of the polyvinylidene fluoride ispreferably 3,000 or more. The upper limit of the weight averagemolecular weight of the polyvinylidene fluoride is preferably 800,000 orless, further preferably 550,000 or less.

The molecular weight distribution (Mw/Mn) of the polyvinylidene fluorideis preferably from 1.1 to 5, more preferably from 1.2 to 4, from theviewpoint of strength and a degree of orientation of a stretched film.Further, the molecular weight distribution is preferably from 1.4 to 3.

The content of polyvinylidene fluoride is preferably more than 0 mass %and 5 mass % or less with respect to the total mass of the polylacticacid-based polymer. When the content of polyvinylidene fluoride is morethan 5 mass %, the piezoelectric polymer material having excellenttransparency may not be obtained. The content of polyvinylidene fluorideis preferably from 0.01 mass % to 5 mass %, more preferably from 0.05mass % to 5 mass %, and further preferably from 0.1 mass % to 2.5 mass%, with respect to the total mass of the polylactic acid-based polymer,from the viewpoint of further increasing the piezoelectric constant.

A single type of polyvinylidene fluoride may be used alone, or two ormore types having different weight average molecular weights Mw,molecular weight distributions (Mw/Mn) or glass transition temperaturesTg may be used in combination.

The weight average molecular weight (Mw) and the molecular weightdistribution (Mw/Mn) of polyvinylidene fluoride can be measured by a GPCmeasuring method.

When the piezoelectric polymer material contains polyvinylidenefluoride, a piezoelectric constant d₁₄ measured at 25° C. by a resonancemethod, as described later, is preferably 10 pC/N or more.

[Other Components]

As necessary, the piezoelectric polymer material in accordance with thepresent embodiment may contain other components such as known resinsincluding polyethylene and polystyrene resins, inorganic fillers such assilica, hydroxyapatite and montmorillonite, and known crystal nucleatingagents such as phthalocyanine, in addition to the helical chiral polymerand optionally contained polyvinylidene fluoride, as long as the effectsof the present embodiment are not undermined.

—Inorganic Filler—

In order to obtain a transparent film in which generation of voids suchas bubbles is suppressed, an inorganic filler such as hydroxyapatite maybe nano-dispersed in the piezoelectric polymer material, for example.However, in order to nano-disperse the inorganic filler, a large amountof energy is necessary to pulverize an aggregate of the inorganicfiller. In addition, when the filler is not nano-dispersed, transparencyof the film may deteriorate. When the piezoelectric polymer material inaccordance with the present embodiment contains an inorganic filler, thecontent of the inorganic filler with respect to the total mass of thepiezoelectric polymer material is preferably less than 1 mass %.

When the piezoelectric polymer material contains a component other thanthe helical chiral polymer, the content of the component other than thehelical chiral polymer is preferably 20 mass % or less, more preferably10 mass % or less, with respect to the total mass of the piezoelectricpolymer material.

—Crystallization Promoting Agent (Crystal Nucleating Agent)—

The crystallization-promoting agent is not particularly limited as longas it can exert an effect of promoting crystallization, but it isdesirable to select a substance having a crystalline structure whoselattice spacing is similar to that of the crystal lattice of polylacticacid. This is because a substance having a closer lattice spacing exertsa higher effect as a nucleating agent.

Examples of the crystallization promoting agent include zincphenylsulfonate, melamine polyphosphate, melamine cyanurate, zincphenylphosphonate, calcium phenylphosphonate and magnesiumphenylphosphonate, which are organic substances, and talc and clay,which are inorganic substances.

Among them, zinc phenylphosphonate is preferred since it has a latticespacing that is most similar to that of polylactic acid, and exerts anexcellent effect of promoting formation of crystals. The crystallizationpromoting agent may be a commercially available product, and specificexamples thereof include zinc phenylphosphonate ECOPROMOTE (manufacturedby Nissan Chemical Industries, Ltd.); and the like.

The content of the crystal nucleating agent is usually from 0.01 to 1.0part by weight, preferably from 0.01 to 0.5 parts by weight, andparticularly preferably from 0.02 to 0.2 parts by weight, with respectto 100 parts by weight of the helical chiral polymer, from the viewpointof achieving a higher crystal promotion effect and maintaining a degreeof biomass. When the content of the crystal nucleating agent is lessthan 0.01 parts by weight, the crystal promotion effect may beinsufficient, while when the content of the crystal nucleating agent ismore than 1.0 part by weight, it may be difficult to control the rate ofcrystallization, thereby causing a decrease in transparency of thepiezoelectric polymer material.

From the viewpoint of transparency, the piezoelectric polymer materialpreferably does not contain a component other than the helical chiralpolymer.

[Structure]

As described later, the piezoelectric polymer material in accordancewith the present embodiment has a structure in which molecules areoriented to a high degree. A molecular orientation ratio MOR is an indexthat indicates the orientation. The MOR (Molecular Orientation Ratio) isa value that indicates the degree of orientation of molecules, and ismeasured by a microwave measuring method as described below.

That is, a sample (film) is placed in the microwave resonance waveguideof a known apparatus for measuring a microwave molecular orientationratio, in such a manner that a plane of the sample (film plane) isperpendicular to a direction in which microwaves travel. Then, while thesample is continuously irradiated with microwaves whose oscillation isin one direction, the sample is rotated at from 0 to 360° in a planeperpendicular to a direction of microwaves to travel, and the MOR iscalculated by measuring the intensity of microwaves that had penetratedthe sample.

The standardized molecular orientation MORc in accordance with thepresent embodiment is a value of MOR obtained at a reference thicknesstc of 50 μm, and may be determined by the following expression:

MORc=(tc/t)×(MOR−1)+1

(tc: reference thickness to be compensated; t: sample thickness)

The standardized molecular orientation MORc may be measured at aresonance frequency of around 4 GHz or 12 GHz by a known molecularorientation meter, such as a microwave-type molecular orientation meterMOA-2012A or MOA-6000, manufactured by Oji Scientific Instruments Co.,Ltd.

The standardized molecular orientation MORc may be controlled byregulating the heat treatment conditions (heating temperature andheating time) prior to stretching a uniaxially stretched film,stretching conditions (stretching temperature and stretching rate), andthe like, as described later.

<Production of Piezoelectric Polymer Material>

The piezoelectric polymer material in accordance with the presentembodiment is obtained from a helical chiral polymer, such as thepreviously explained polylactic acid-based polymer, or from a mixture ofa helical chiral polymer with other optional components.

The mixture is preferably melt-kneaded.

Specifically, for example, when two kinds of helical chiral polymers aremixed or when a helical chiral polymer is mixed with an inorganic filleror a crystal nucleating agent as described above, the helical chiralpolymer to be mixed may be melt-kneaded at a mixer revolution rate of 30rpm to 70 rpm and a temperature of from 180° C. to 250° C. for from 5minutes to 20 minutes, with a melt-kneading machine (LABO PLASTOMILLMIXER, manufactured by Toyo Seiki Seisaku-sho, Ltd.), thereby obtaininga blend of plural kinds of helical chiral polymers or a blend of ahelical chiral polymer with other components such as an inorganicfiller.

<Methods for Producing Piezoelectric Polymer Material>

—First Method—

The piezoelectric polymer material in accordance with the presentembodiment may be produced, for example, by a production methodincluding a first step of heating a sheet in an amorphous statecontaining a helical chiral polymer to obtain a preliminarilycrystallized sheet, and a second step of stretching the preliminarilycrystallized sheet mainly in a uniaxial direction.

Generally, as a force applied to a film during stretching is increased,orientation of the helical chiral polymer is promoted and apiezoelectric constant is increased, whereby crystallization is promotedand the crystal size is increased. As a result, the degree of haze tendsto be increased. Also, a dimension deformation rate tends to increasedue to an increase in internal stress. When a force is simply applied tothe film, crystals that are not oriented, such as spherulites, areformed. Crystals with low orientation, such as spherulites, are lesslikely to contribute to an increase in the piezoelectric constant, whileincreasing the haze. Therefore, in order to form a film that is high inpiezoelectric constant but low in haze and dimension deformation rate,it is necessary to form oriented crystals that contribute to an increasein the piezoelectric constant, which crystals having a size that issmall enough not to increase the haze, with high efficiency.

In the first method for producing the piezoelectric polymer materialaccording to the present invention, for example, inside of a sheet issubjected to preliminary crystallization to form microscopic crystals,and then the sheet is stretched. In this way, a force can be efficientlyapplied to a polymer portion among microscopic crystals, in whichcrystallinity is low, whereby helical chiral polymers can be efficientlyoriented in a main stretching direction. More specifically, whilemicroscopic oriented crystals are generated in a polymer portion amongmicroscopic crystals having low crystallinity, spherulites that havebeen generated during the preliminary crystallization are broken, andlamella crystals that form the spherulites are oriented in a stretchingdirection in the form of beads linked to tie molecular chains, whereby adesired value of MORc can be obtained. As a result, a sheet that is lowin haze and dimension deformation rate can be obtained without greatlydecreasing the piezoelectric constant.

In order to control the standardized molecular orientation MORe, it isimportant to regulate the time and the temperature for the heattreatment in the first step, and to regulate the rate and thetemperature of stretching in the second step.

As previously described, the helical chiral polymer is a polymer thathas a helical molecular structure and molecular optical activity, andthe sheet that is in an amorphous state and contains the helical chiralpolymer may be commercially obtained or may be prepared by a knownfilm-molding means, such as extrusion molding. The sheet in an amorphousstate may be single- or multi-layered.

[First Step (Preliminary Crystallization Step)]

The preliminarily crystallized sheet may be obtained by causingcrystallization of a sheet that is in an amorphous state and contains ahelical chiral polymer, by heating the sheet.

Specifically, 1) a sheet that has been obtained by crystallizing anamorphous sheet by heating the same may be subjected to the subsequentstretching step (second step) by setting the sheet to an stretchingmachine (off-line heat treatment), or 2) an amorphous sheet that has notbeen crystallized by heating may be set in a stretching machine, andthen subjected to heating for preliminary crystallization and stretching(in-line heat treatment).

The heat treatment temperature T for carrying out preliminarilycrystallization of the sheet that is in an amorphous state and containsa helical chiral polymer is not particularly limited. However, in orderto improve piezoelectricity and transparency of a piezoelectric polymermaterial, the heat treatment temperature is preferably determined suchthat a relationship represented by the following expression is satisfiedand the crystallinity is in a range of from 10 to 70%.

Tg≦T≦Tg+40° C.

(Tg represents the glass transition temperature of the helical chiralpolymer material)

The heat treatment time for preliminary crystallization may be adjustedsuch that a desired crystallinity is achieved and the product of thestandardized molecular orientation MORc of the piezoelectric polymermaterial after the stretching (after the second step) and thecrystallinity of the piezoelectric polymer material after the stretchingis preferably 40 or more, more preferably 75 or more, further preferably100 or more, yet further preferably 120 or more. For example, thecrystallinity of the piezoelectric polymer material after the stretchingmay be from 40 to 700, from 100 to 700, from 125 to 650, or from 250 to350. If the heat treatment time is extended, crystallinity after thestretching is increased and the standardized molecular orientation MORcafter the stretching is also increased. If the heat treatment time isshortened, crystallinity after the stretching is decreased and thestandardized molecular orientation MORc after the stretching is alsodecreased.

When crystallinity of the preliminarily crystallized sheet prior tostretching is increased, the sheet becomes harder and a greaterstretching stress is applied to the sheet, and therefore the orientationbecomes stronger even in a region inside the sheet in whichcrystallinity is relatively low. As a result, the standardized molecularorientation MORc after the stretching is increased. Conversely, when thecrystallinity of the preliminarily crystallized sheet prior tostretching is decreased, the sheet becomes softer and a smallerstretching stress is applied to the sheet, and therefore the orientationbecomes weaker even in a region inside the sheet in which crystallinityis relatively low. As a result, the standardized molecular orientationMORc after the stretching is decreased.

The heat treatment time may vary depending on the heat treatmenttemperature, the thickness of a sheet, the molecular weight of a resinthat forms the sheet, and the type or the amount of an additive or thelike. In addition, when preheating is carried out prior to stretching(second step) at a temperature at which an amorphous sheet iscrystallized, the time for heat treatment in which the sheet issubstantially crystallized corresponds to the total of the preheatingtime and the heat treatment time for preliminary crystallization that iscarried out prior to the preheating.

The time for carrying out heat treatment of a sheet that is in anamorphous state is typically from 5 seconds to 60 minutes, and may befrom 1 minute to 30 minutes from the viewpoint of stabilizing theproduction conditions. For example, when a sheet in an amorphous statecontaining a polylactic resin as a helical chiral polymer is subjectedto preliminary crystallization, the heating is preferably performed atfrom 60° C. to 170° C. for 5 seconds to 60 minutes, which may be from 1minute to 30 minutes.

In order to efficiently provide the stretched sheet withpiezoelectricity, transparency and high dimensional stability, it isimportant to adjust the crystallinity of the preliminarily crystallizedsheet prior to stretching the same. The reason why piezoelectricity anddimensional stability are improved by stretching is considered to bethat a stress created by stretching is concentrated on a region with arelatively high crystallinity of the preliminarily crystallized sheet,which region is presumed to be in a spherulite state, while thepiezoelectric characteristic d₁₄ is increased as the spherulites arebroken and oriented. In addition, a stretching stress is applied also toa region having relatively low crystallinity via the spherulites,whereby orientation is promoted and the piezoelectric characteristic d₁₄is increased.

The crystallinity of the stretched sheet is preferably 20 or more, morepreferably 25 or more, further preferably 30 or more, yet furtherpreferably 40 or more. For example, the crystallinity of the stretchedsheet may be from 20 to 80%, 40 to 80%, or from 40 to 70%. Therefore,the crystallinity of the preliminarily crystallized sheet immediatelybefore the stretching is from 1 to 70%, preferably from 3 to 70%, morepreferably from 10 to 60%, and further preferably from 15 to 50%.

The crystallinity of the preliminarily crystallized sheet can bemeasured in a similar manner to the measurement of crystallinity of thepiezoelectric polymer material in accordance with the present embodimentafter the stretching.

The thickness of the preliminarily crystallized sheet, which isdetermined mainly by the thickness and the stretching ratio of thepiezoelectric polymer material which is to be obtained by the stretchingin the second step, is preferably from 50 to 1,000 nm, more preferablyfrom around 200 to 800 μm.

[Second Step (Stretching Step)]

The method of stretching in the stretching step, which corresponds tothe second step, is not particularly limited, and various stretchingmethods such as uniaxial stretching, biaxial stretching, and solid-phasestretching as described later may be used.

By stretching a piezoelectric polymer material, a piezoelectric polymermaterial having a large principal plane can be obtained.

In the present specification, “principal plane” refers to a plane havinga largest area among surfaces of a piezoelectric polymer material. Thepiezoelectric polymer material in accordance with the present embodimentmay have two or more principal planes. For example, when thepiezoelectric polymer material has a plate-like shape with two planes Aof 10 mm×0.3 mm, two planes B of 3 mm×0.3 mm, and two planes C of 10mm×3 mm, respectively, the principal planes of the piezoelectric polymermaterial are planes C, and the piezoelectric polymer material has twoprincipal planes.

In the present embodiment, a principal plane having a large area refersto a principal plane having an area of 5 mm² or more, preferably 10 mm²or more.

In addition, “solid-phase stretching” refers to “stretching carried outat a temperature that is higher than the glass transition temperature Tgof the piezoelectric polymer material and is lower than the meltingpoint Tm of the piezoelectric polymer material, and under a compressivestress of from 5 MPa to 10,000 MPa”. Under these conditions,piezoelectricity of the piezoelectric polymer material can be furtherimproved, and transparency and elasticity can be improved.

By subjecting a piezoelectric polymer material to solid-phase stretchingor mainly uniaxial stretching, it is presumed that molecular chains of apolylactic acid-based polymer contained in the piezoelectric polymermaterial are oriented in one direction and aligned at high density,thereby achieving an even higher piezoelectricity.

In the present specification, the glass transition temperature Tg [° C.]of the piezoelectric polymer material and the melting point Tm [° C.] ofthe piezoelectric polymer material refer to a glass transitiontemperature (Tg) that is obtained as an inflection point, and atemperature (Tm) confirmed as a peak value in an endothermic reaction,respectively, from a melt endothermic curve obtained by increasing thetemperature of the piezoelectric polymer material at a rate of 10°C./min with a differential scanning calorimeter (DSC).

The stretching temperature of the piezoelectric polymer material ispreferably in a range higher than the glass transition temperature ofthe piezoelectric polymer material by approximately from 10° C. to 20°C., when the piezoelectric polymer material is stretched only by atensile force, such as uniaxial stretching or biaxial stretching.

In the case of solid-phase stretching, the compressive stress ispreferably from 50 MPa to 5,000 MPa, more preferably from 100 MPa to3,000 MPa.

The stretching ratio during stretching is preferably from 3 times to 30times, more preferably from 4 times to 15 times.

The solid-phase stretching of the preliminarily crystallized sheet isperformed, for example, by pinching the piezoelectric polymer materialbetween rolls or burettes and applying a pressure thereto.

When the preliminarily crystallized sheet is stretched, preheating maybe performed immediately prior to performing stretching so that thesheet can be easily stretched. Since the preheating is performedgenerally for the purpose of softening the sheet prior to stretching thesame to facilitate the stretching, it is usually performed under theconditions in which the sheet is not hardened by causing crystallizationof the same. However, in the present embodiment, preliminarycrystallization is performed prior to the stretching, as describedabove. Therefore, the preheating may be performed also as a process forpreliminary crystallization. Specifically, the preheating can beperformed also as the preliminary crystallization by carrying out theprocess at a higher temperature for a longer time in order to conform tothe temperature and the time for preliminary crystallization, ascompared with a temperature and a time that are ordinarily employed inthe preheating process.

[Annealing Treatment]

From the viewpoint of improving the piezoelectric constant, it ispreferred to subject a piezoelectric polymer material that has beenstretched to a heat treatment (hereinafter, also referred to as an“annealing treatment”).

The temperature for the annealing treatment is generally preferably from80° C. to 160° C., further preferably from 100° C. to 155° C.

The method of temperature application in the annealing treatment is notparticularly limited, and examples thereof include direct heating with ahot blast heater or an infrared heater, immersing the piezoelectricpolymer material in a heated liquid such as heated silicone oil, and thelike.

In this process, if deformation of the piezoelectric polymer materialoccurs due to linear expansion, it becomes difficult to produce a filmthat is flat in terms of practical use. Therefore, it is preferable toapply a temperature while applying a tensile stress (e.g., from 0.01 MPato 100 Mpa) to the piezoelectric polymer material in order to preventsagging of the piezoelectric polymer material.

The temperature application time during the annealing treatment ispreferably from 1 second to 60 minutes, more preferably from 1 second to300 seconds, further preferably from 1 second to 60 seconds. When thetime for annealing is longer than 60 minutes, the orientation degree maydecrease due to a growth of spherulites from molecular chains of anamorphous moiety at a higher temperature than the glass transitiontemperature of the piezoelectric polymer material, thereby causingdeterioration in piezoelectricity.

The piezoelectric polymer material that has been subjected to theannealing treatment as described above is preferably quenched after theannealing treatment. In the annealing treatment, “quenching” refers tocooling the piezoelectric polymer material that has been subjected tothe annealing treatment, to a temperature at least equal to or lowerthan the glass transition temperature Tg, by immersing the piezoelectricpolymer material in ice water or the like immediately after theannealing treatment, without conducting any treatments between theannealing and the immersion.

Examples of the method for quenching include a method of immersing thepiezoelectric polymer material that has been subjected to the annealingtreatment in a refrigerant such as water, ice water, ethanol, ethanol ormethanol in which dry ice is placed, or liquid nitrogen, and a method ofspraying a liquid having a low vapor pressure to perform cooling bylatent heat of vaporization. When it is desired to cool thepiezoelectric polymer material in a serial manner, the piezoelectricpolymer material can be rapidly cooled by contacting a metal roll havinga temperature that is controlled to be not more than the glasstransition temperature Tg of the piezoelectric polymer material.

The number of times of cooling may be only one or two or more. Theannealing and the cooling may be alternately repeated.

—Second Method—

The piezoelectric polymer material in accordance with the presentembodiment may be produced by a method including a step of stretching asheet containing a helical chiral polymer mainly in a uniaxialdirection, a step of carrying out annealing, and a hydrolysis step.

The step of stretching mainly in the uniaxial direction and the step ofcarrying out annealing are similar to the stretching step and theannealing step carried out in the first method, respectively, andexplanation thereof will be omitted.

[Hydrolysis Step]

The hydrolysis step in accordance with the present embodiment is notparticularly limited as long as it is a method in which the weightaverage molecular weight of the piezoelectric polymer material isdecreased, and examples of the method include a method of immersing thepiezoelectric polymer material in warm water, a method of treating thepiezoelectric polymer material in a thermostat-humidistat bath undernormal pressure, and a method of treating the piezoelectric polymermaterial with vapor at high temperature under high pressure. Ultrasonicwaves or microwaves may be used for accelerating a hydrolysis reaction.A catalyst such as an acid, an alkali or an enzyme may also be used.

In the present embodiment, the number of times for performing stretchingmainly in a uniaxial direction, annealing and hydrolysis, and the orderof performing these steps, are not particularly limited. However, it ispreferred to perform one or more cycles of performing stretching mainlyin a uniaxial direction, annealing and hydrolysis, and then performing afurther annealing.

The hydrolysis step may be performed before the first annealing step orafter the first stretching step. In addition, the second stretching isnot essential.

In the present embodiment, the weight average molecular weight of thepiezoelectric polymer material is decreased during the hydrolysis step,and the degree of decrease is represented by a molecular weightremaining rate as defined by the following Expression (1). The molecularweight remaining rate is preferably 50% or more and less than 90%.

Molecular weight remaining rate=[Mw2/Mw1]×100(%)]  Expression (1)

(Mw1 represents the weight average molecular weight of the piezoelectricpolymer material prior to the hydrolysis treatment, and Mw2 representsthe weight average molecular weight of the piezoelectric polymermaterial after the final annealing treatment.)

The weight average molecular weight of the piezoelectric polymermaterial is measured by a GPC measuring method, as described above.

In the present embodiment, it is presumed that by subjecting thepiezoelectric polymer material to the step of stretching mainly in auniaxial direction and the annealing step, molecular chains in thepolylactic acid-based polymer contained in the piezoelectric polymermaterial are oriented in one direction, and oriented crystals that arealigned at high density are generated. Further, by performinghydrolysis, it is presumed that the molecular chains in an amorphousmoiety remaining among the crystals are partially severed and untangled.As a result, it is presumed that a further growth of the orientedcrystals is promoted during the subsequent stretching and annealingsteps, and an even higher piezoelectricity can be obtained. It isfurther presumed that a portion with high crystallinity (a region thatcontributes to piezoelectricity) is highly resistant to hydrolysis anddoes not change significantly during hydrolysis, whereas a portion withlow crystallinity (a region that does not contribute topiezoelectricity) is susceptible to hydrolysis, and thus is oriented bythe treatment to contribute to piezoelectricity.

<Physical Properties of Piezoelectric Polymer Material>

The piezoelectric polymer material in accordance with the presentembodiment has a high piezoelectric constant (piezoelectric constant d₁₄measured by a displacement method at 25° C. of 1 pm/V or more), andexhibits excellent transparency and dimensional stability.

[Piezoelectric Constant (Displacement Method)]

In the present embodiment, the piezoelectric constant of thepiezoelectric polymer material refers to a value measured by a method asdescribed below.

The piezoelectric polymer material is cut into a size of 40 mm in astretching direction (MD direction) and 40 mm in a directionperpendicular to the stretching direction (TD direction), respectively,thereby preparing a rectangular test piece.

The resultant test piece is set on a test bench of a sputtering thinfilm deposition system JSP-8000, manufactured by Ulvac, Inc., and theinside of a coater chamber is vacuumed with a rotary pump (for example,10⁻³ Pa or less). Thereafter, sputtering is carried out on one face ofthe test piece for 500 seconds at an applied voltage of 280 V and asputtering current of 0.4 A with an Ag (silver) target. Then, sputteringis carried out on the other face of the test piece under the sameconditions for 500 seconds, thereby coating both faces of the test piecewith Ag to form Ag conductive layers.

The test piece of 40 mm×40 mm having Ag conductive layers on both facesis cut in a size of 32 mm in a direction of 45° with respect to thestretching direction (MD direction) of the piezoelectric polymermaterial, and 5 mm in the direction perpendicular to the direction of45°, thereby obtaining a rectangular film of 32 mm×5 mm. This was usedas a sample for measuring the piezoelectric constant.

A difference distance between a maximal value and a minimum value of thedisplacement of the film, which occurred upon application of analternating voltage of 10 Hz and 300 Vpp to the sample, was measured bya laser spectral-interference displacement meter SI-1000, manufacturedby Keyence Corporation. The value obtained by dividing the measureddisplacement (mp-p) by the reference length of the film, which was 30mm, was used as an amount of deformation, and a value obtained bymultiplying a value, obtained by dividing the amount of deformation byan electric field intensity ((applied voltage (V))/(film thickness))applied to the film, by 2, was used as the piezoelectric constant d₁₄.

A higher piezoelectric constant results in a greater displacement of thematerial with respect to a voltage applied to the piezoelectric polymermaterial, or conversely, a voltage generated with respect to a forceapplied to the piezoelectric polymer material, which is advantageous asa piezoelectric polymer material.

Specifically, the piezoelectric constant d₁₄ as measured by adisplacement method at 25° C. is preferably 1 pm/V or more, morepreferably 2 pm/V or more, further preferably 3 pm/V or more, yetfurther preferably 4 pm/V or more, yet further preferably 5 pm/V ormore, yet further preferably 6 pm/V or more, and yet further preferably8 pm/V or more.

The upper limit of the piezoelectric constant is not particularlylimited, but is preferably 50 pm/V or less, and more preferably 30 pm/Vor less, in the case of a piezoelectric material employing a helicalchiral polymer, from the viewpoint of a balance with transparency asdescribed below, etc.

[Crystallinity]

The crystallinity of the piezoelectric polymer material is determined bya DSC method, and the crystallinity of the piezoelectric polymermaterial in accordance with the present embodiment is preferably 20 ormore, for example, from 25 to 80%, from 30 to 80%, from 40 to 80% orfrom 50 to 70%. If the crystallinity is within the range, the balancebetween piezoelectricity and transparency of the piezoelectric polymermaterial may be favorable, and whitening or breaking is less likely tooccur during stretching, thereby facilitating the production of apiezoelectric polymer material.

[Transparency (Internal Haze)]

The transparency of the piezoelectric polymer material may be evaluatedby, for example, visual observation or haze measurement. Inpiezoelectric polymer materials, the transmission haze with respect tovisible light is preferably 50% or less, more preferably from 0.0% to40%, further preferably 0.05 to 30%. In the present specification, thehaze is a value as measured with a piezoelectric polymer material havinga thickness of 0.05 mm at 25° C., using a haze meter (manufactured byTokyo Denshoku Co., Ltd.; TC-HIII DPK) in accordance with JIS-K7105.Details of the measuring method are described in the Examples describedlater. The haze of the piezoelectric polymer material is preferablylower, but is preferably from 0.01% to 10%, further preferably from 0.1%to 5%, from the viewpoint of a balance with the piezoelectric constantand the like. The term “haze” or “transmission haze” in the presentinvention refers to an internal haze of the piezoelectric polymermaterial according to the present invention. The internal haze is a hazefrom which a haze that originates from the shape of an external surfaceof a piezoelectric polymer material is excluded, as described in theExamples below.

[Standardized Molecular Orientation MORc]

The piezoelectric polymer material in accordance with the presentembodiment preferably has a standardized molecular orientation MORc offrom 2 to 15.0, from 3.5 to 15.0, more preferably from 4.0 to 15.0,further preferably from 6.0 to 10.0, and further more preferably from 7to 10.0. If the standardized molecular orientation MORc is in the rangeof from 2.0 to 15.0, more polylactic acid molecular chains are arrangedin a stretching direction, whereby a rate of generation of orientedcrystals can be increased and high piezoelectricity can be achieved.

[Product of Standardized Molecular Orientation MORc and Crystallinity]

The product of the crystallinity and the standardized molecularorientation MORc of the piezoelectric polymer material is preferably 40or more, more preferably 75 or more, further preferably 100 or more, yetfurther preferably 120 or more. For example, the crystallinity may befrom 40 to 700, from 125 to 650, or from 250 to 350. If the product ofthe crystallinity and the standardized molecular orientation MORc of thepiezoelectric polymer material is in the range of 40 or more, thebalance between piezoelectricity and transparency of the piezoelectricpolymer material is favorable and the dimensional stability is high,whereby the piezoelectric polymer material can be suitably used as apiezoelectric element as described later.

Since the piezoelectric polymer material in accordance with the presentembodiment is a piezoelectric material having a high piezoelectricconstant d₁₄ and excellent transparency and dimensional stability, asdescribed above, the piezoelectric polymer material can be used invarious fields including speakers, headphones, microphones, hydrophones,ultrasonic transducers, ultrasonic application measurement instruments,piezoelectric vibrators, mechanical filters, piezoelectric transformers,delay apparatuses, sensors, acceleration sensors, shock sensors,vibration sensors, pressure-sensitive sensors, tactile sensors, electricfield sensors, sound pressure sensors, displays, fans, pumps, variablefocus mirrors, sound insulating materials, soundproof materials,keyboards, acoustic instruments, information processing machines,measuring instruments and medical instruments.

In that case, the piezoelectric polymer material in accordance with thepresent embodiment is preferably used as a piezoelectric element havingat least two planes that are provided with an electrode. It is enough ifthe electrodes are provided to at least two planes of the piezoelectricpolymer material. Materials for the electrodes are not particularlylimited, and include, for example, ITO, ZnO, IZO (registered trademark),conductive polymers and the like.

In particular, when an electrode is provided on a principal plane of thepiezoelectric polymer material, the electrode preferably hastransparency. In the present specification, when the electrode has aninternal haze of 20% or less (total light transmittance of 80% or more),the electrode is defined to have transparency.

The piezoelectric element formed from the piezoelectric polymer materialin accordance with the present embodiment may be applied to theabove-described various piezoelectric devices, such as the speakers andtouch panels. In particular, a piezoelectric element provided with anelectrode having transparency is suitably applied speakers, touchpanels, actuators and the like.

<Piezoelectric Polymer Material in Accordance with the SecondEmbodiment>

The piezoelectric polymer material in accordance with the secondembodiment is a piezoelectric polymer material including a polylacticacid-based polymer and polyvinylidene fluoride, wherein a content of thepolyvinylidene fluoride is from more than 0 mass % to 5 mass % withrespect to the total mass of the polylactic acid-based polymer, andwherein a piezoelectric constant d₁₄ measured by a resonance method at25° C. is 10 pC/N or more.

The piezoelectric polymer material in accordance with the presentembodiment may contain polyvinylidene fluoride at a rate of more than 0mass % to 5 mass % with respect to the total mass of the polylacticacid-based polymer.

Since the piezoelectric polymer material contains polyvinylidenefluoride together with the polylactic acid-based polymer, it has a highpiezoelectric constant and excellent transparency. It is presumed thatpolyvinylidene fluoride functions as a crystal nucleating agent.

The weight average molecular weight (Mw) of the polyvinylidene fluorideis preferably from 3,000 to 1,000,000.

When the lower limit of the weight average molecular weight is 3,000 ormore, the piezoelectric polymer material exhibits excellent mechanicalstrength, and when the upper limit is 1,000,000 or less, molding (suchas extrusion) of the piezoelectric polymer material becomes easy. Thelower limit of the weight average molecular weight of polyvinylidenefluoride is preferably 3,000 or more. The upper limit of the weightaverage molecular weight of polyvinylidene fluoride is preferably800,000 or less, further preferably 550,000 or less.

The molecular weight distribution (Mw/Mn) of polyvinylidene fluoride ispreferably from 1.1 to 5, more preferably from 1.2 to 4, from theviewpoint of strength and orientation degree of a stretched film. Themolecular weight distribution is preferably further preferably from 1.4to 3.

The content of polyvinylidene fluoride is from more than 0 mass % to 5mass % with respect to the total mass of the polylactic acid-basedpolymer. When the content is more than 5 mass %, the piezoelectricpolymer material may not exhibit favorable transparency. The content ispreferably from 0.01 mass % to 5 mass %, more preferably from 0.05 mass% to 5 mass %, and further preferably from 0.1 mass % to 2.5 mass %,with respect to the total mass of the polylactic acid-based polymer,from the viewpoint of further increasing the piezoelectric constant.

Only a single kind of polyvinylidene fluoride may be used, or two ormore kinds having different weight average molecular weights Mw,molecular weight distributions (Mw/Mn) or glass transition temperaturesTg may be used in combination.

The weight average molecular weight (Mw) and the molecular weightdistribution (Mw/Mn) of polyvinylidene fluoride can be measured by a GPCmeasuring method, as described above.

[Other Components]

The piezoelectric polymer material in accordance with the presentembodiment may also contain other components such as known resinsincluding polyethylene and polystyrene resins, inorganic compounds suchas silica, hydroxyapatite and montmorillonite, and known crystalnucleating agents such as phthalocyanine, in addition to the polylacticacid-based polymers and polyvinylidene fluoride, as long as the effectsof the present embodiment are not undermined.

—Inorganic Filler—

In order to obtain a transparent film in which generation of voids suchas bubbles is suppressed, an inorganic filler such as hydroxyapatite maybe nano-dispersed in the piezoelectric polymer material, for example.However, in order to nano-disperse the inorganic filler, a large amountof energy is necessary to pulverize an aggregate of the inorganicfiller. In addition, when the filler is not nano-dispersed, transparencyof the film may deteriorate. When the piezoelectric polymer material inaccordance with the present embodiment contains an inorganic filler, thecontent of the inorganic filler with respect to the total mass of thepiezoelectric polymer material is preferably less than 1 mass %.

When the piezoelectric polymer material contains a component other thanthe polylactic acid-based polymer and polyvinylidene fluoride, thecontent of the component other than the polylactic acid-based polymerand polyvinylidene fluoride is preferably 20 mass % or less, morepreferably 10 mass % or less, with respect to the total mass of thepiezoelectric polymer material.

The piezoelectric polymer material preferably does not containcomponents other than the polylactic acid-based polymer andpolyvinylidene fluoride, from the viewpoint of a piezoelectric constantand transparency.

<Production of Piezoelectric Polymer Material>

The piezoelectric polymer material in accordance with this embodiment isobtained by mixing the polylactic acid-based polymer and polyvinylidenefluoride at a ratio as described above, and other components asnecessary.

The mixture is preferably melt-kneaded.

Specifically, for example, a blend of the polylactic acid-based polymerand polyvinylidene fluoride can be obtained by melt-kneading with amelt-kneading machine [manufactured by Toyo Seiki Seisaku-sho, Ltd.;LABO PLASTOMILL MIXER] under the conditions of a mixer revolution speedof 30 rpm to 70 rpm and 180° C. to 250° C. for 5 minutes to 20 minutes.

<Molding of Piezoelectric Polymer Material>

The piezoelectric polymer material is preferably made into a moldedproduct that has been subjected to a stretching treatment. Thestretching method is not particularly limited, and various stretchingmethods such as uniaxial stretching, biaxial stretching, and solid-phasestretching as described later may be used.

By subjecting the piezoelectric polymer material to stretching, apiezoelectric polymer material having a large area of a principal planecan be obtained.

In the present specification, “principal plane” refers to a plane havinga largest area among surfaces of a piezoelectric polymer material. Thepiezoelectric polymer material in accordance with the present embodimentmay have two or more principal planes. For example, when thepiezoelectric polymer material has a plate-like shape with two planes Λof 10 mm×0.3 mm, two planes B of 3 mm×0.3 mm, and two planes C of 10mm×3 mm, respectively, the principal planes of the piezoelectric polymermaterial are planes C, and the piezoelectric polymer material has twoprincipal planes.

In the present embodiment, a principal plane having a large area refersto a principal plane having an area of 5 mm² or more, preferably 10 mm²or more.

In addition, “solid-phase stretching” refers to “stretching carried outat a temperature that is higher than the glass transition temperature Tgof the piezoelectric polymer material and is lower than the meltingpoint Tm of the piezoelectric polymer material, and under a compressivestress of from 5 MPa to 10,000 MPa”. Under these conditions,piezoelectricity of the piezoelectric polymer material can be furtherimproved, and transparency and elasticity can be improved.

By subjecting a piezoelectric polymer material to solid-phasestretching, it is presumed that molecular chains of a polylacticacid-based polymer contained in the piezoelectric polymer material areoriented in one direction and aligned at high density, thereby achievingan even higher piezoelectricity.

In the present specification, the glass transition temperature Tg [° C.]of the piezoelectric polymer material and the melting point Tm [° C.] ofthe piezoelectric polymer material refer to a glass transitiontemperature (Tg) that is obtained as an inflection point, and atemperature (Tm) confirmed as a peak value in an endothermic reaction,respectively, from a melt endothermic curve obtained by increasing thetemperature of the piezoelectric polymer material at a rate of 10°C./min with a differential scanning calorimeter (DSC).

The stretching temperature of the piezoelectric polymer material ispreferably in a range higher than the glass transition temperature ofthe piezoelectric polymer material by approximately 10° C. to 20° C.,when the piezoelectric polymer material is stretched only by a tensileforce, such as uniaxial stretching or biaxial stretching.

The compressive stress is preferably from 50 MPa to 5,000 MPa, morepreferably from 100 MPa to 3,000 MPa.

The stretching ratio during stretching is preferably from 3 times to 30times, more preferably from 4 times to 15 times.

The stretching of the piezoelectric polymer material is performed by,for example, pinching the piezoelectric polymer material between rollsor burettes and applying a pressure thereto. When the stretching iscarried out with burettes, it is preferred to preheat the piezoelectricpolymer material to a temperature of from 60° C. to 170° C. for 1 minuteto 60 minutes, prior to stretching the piezoelectric polymer material byapplying a pressured to the piezoelectric polymer material pinchedbetween the burettes.

The temperature of the heating treatment prior to stretching ispreferably from 100° C. to 160° C., and the heating time is preferablyfrom 5 minutes to 30 minutes.

From the viewpoint of improving the piezoelectric constant, it ispreferred to subject a piezoelectric polymer material that has beenstretched to a heat treatment (hereinafter, also referred to as an“annealing treatment”).

The temperature for the annealing treatment is generally preferably from80° C. to 160° C., further preferably from 100° C. to 155° C.

The method of temperature application in the annealing treatment is notparticularly limited, and examples thereof include direct heating with ahot blast heater or an infrared heater, immersing the piezoelectricpolymer material in a heated liquid such as heated silicone oil, and thelike.

In this process, if deformation of the piezoelectric polymer materialoccurs due to linear expansion, it becomes difficult to produce a filmthat is flat in terms of practical use. Therefore, it is preferable toapply a temperature while applying a tensile stress (e.g., from 0.01 MPato 100 Mpa) to the piezoelectric polymer material in order to preventsagging of the piezoelectric polymer material.

The temperature application time during the annealing treatment ispreferably from 1 second to 300 seconds, further preferably from 1second to 60 seconds. When the time for annealing is longer than 300seconds, the orientation degree may decrease due to a growth ofspherulites from molecular chains of an amorphous moiety at a highertemperature than the glass transition temperature of the piezoelectricpolymer material, thereby causing deterioration in piezoelectricity.

The piezoelectric polymer material that has been subjected to theannealing treatment as described above is preferably quenched after theannealing treatment. In the annealing treatment, “quenching” refers tocooling the piezoelectric polymer material that has been subjected tothe annealing treatment, to a temperature at least equal to or lowerthan the glass transition temperature Tg, by immersing the piezoelectricpolymer material in ice water or the like immediately after theannealing treatment, without conducting any treatments between theannealing and the immersion.

Examples of the method for quenching include a method of immersing thepiezoelectric polymer material that has been subjected to the annealingtreatment in a refrigerant such as water, ice water, ethanol, ethanol ormethanol in which dry ice is placed, or liquid nitrogen, and a method ofspraying a liquid having a low vapor pressure to perform cooling bylatent heat of vaporization. When it is desired to cool thepiezoelectric polymer material in a serial manner, the piezoelectricpolymer material can be rapidly cooled by contacting a metal roll havinga temperature that is controlled to be not more than the glasstransition temperature Tg of the piezoelectric polymer material.

The number of times of cooling may be only one or two or more. Theannealing and the cooling may be alternately repeated.

<Physical Properties of Piezoelectric Polymer Material>

The piezoelectric polymer material in accordance with the presentembodiment has a high piezoelectric constant (piezoelectric constant d₁₄as measured by a resonance method of 10 pC/N or more) and excellenttransparency.

[Piezoelectric Constant (Resonance Method)]

In the present embodiment, the piezoelectric constant of thepiezoelectric polymer material refers to a value measured as describedbelow.

The piezoelectric polymer material is cut into a size of 32 mm in astretching direction (MD direction) and 30 mm in a directionperpendicular to the stretching direction (TD direction), therebypreparing a rectangular test piece.

The resultant test piece is set on a test bench of QUICK COATER SC-701,manufactured by Sanyu Electron Co., Ltd., and the inside of a coaterchamber is vacuumed (for example, 10⁻³ Pa or less) with a rotary pump.Thereafter, one face of the test piece is subjected to sputtering for 3minutes with Au (gold) target at a sputtering current of 4 mA.Subsequently, the other face of the test piece is subjected tosputtering under the same conditions for 3 minutes, thereby forming anAu conductive layer on both faces of the test piece.

The test piece of 32 mm×30 mm, having Au conductive layers on bothsides, is cut into a size of 10 mm in a stretching direction (MDdirection) of the piezoelectric polymer material and 9 mm in a directionperpendicular to the stretching direction (TD direction). This is usedas a sample for a resonance/anti-resonance method measurement.

A resonance curve of impedance that appears in a band region of from 50kHz to 100 kHz is measured with an impedance analyzer HP4194A,manufactured by Yokogawa-Hewlett-Packard Company. From the obtainedresonance curve of impedance and a relative dielectric constant ∈r, apiezoelectric constant d₁₄ is calculated by a method described in Jpn.J. Appl. Phys. Vol. 37 (1998) pp. 3374-3376, part 1, No. 6A, June 1998.

The obtained piezoelectric constant is used as the piezoelectricconstant of the piezoelectric polymer material.

The relative dielectric constant ∈_(r) is calculated by the followingExpression (A) from a capacitance C [F] measured with an LCR meterHP4284A, manufactured by Hewlett-Packard Company, for the sample forresonance/anti-resonance method measurement.

$\begin{matrix}{ɛ_{r} = \frac{C \times d}{ɛ_{0} \times S}} & {{Expression}\mspace{14mu} (A)}\end{matrix}$

In the Expression (A), definitions of ∈₀, C, d, ∈_(r) and S are asfollows.

∈_(r): relative dielectric constant of sample forresonance/anti-resonance method measurement

C: capacitance [F] of sample for resonance/anti-resonance methodmeasurement

d: thickness [m] of sample for resonance/anti-resonance methodmeasurement

∈₀: dielectric constant of vacuum

S: area [m²] of sample for resonance/anti-resonance method measurement

[Transparency (Haze)]

The transparency of the piezoelectric polymer material may be evaluatedby, for example, visual observation or haze measurement. Inpiezoelectric polymer materials, the haze is preferably 50 or less, morepreferably from 0.0 to 40, further preferably from 0.05 to 30. In thepresent specification, the haze is a value as measured with apiezoelectric polymer material having a thickness of 0.05 mm at 25° C.,using a haze meter (manufactured by Tokyo Denshoku Co., Ltd.; TC-HIIIDPK) in accordance with JIS-K7105. Details of the measuring method aredescribed in the Examples described later. The haze of the piezoelectricpolymer material is preferably from 0.1 to 10, further preferably from0.1 to 5.

Since the piezoelectric polymer material in accordance with the presentembodiment is a piezoelectric material having a high piezoelectricconstant d₁₄ and excellent transparency, as described above, thepiezoelectric polymer material can be used in various fields includingspeakers, headphones, microphones, hydrophones, ultrasonic transducers,ultrasonic application measurement instruments, piezoelectric vibrators,mechanical filters, piezoelectric transformers, delay apparatuses,sensors, acceleration sensors, shock sensors, vibration sensors,pressure-sensitive sensors, tactile sensors, electric field sensors,sound pressure sensors, displays, fans, pumps, variable focus mirrors,sound insulating materials, soundproof materials, keyboards, acousticinstruments, information processing machines, measuring instruments andmedical instruments.

In that case, the piezoelectric polymer material in accordance with thepresent embodiment is preferably used as a piezoelectric element havingat least two planes provided with an electrode. It is enough if theelectrodes are provided to at least two planes of the piezoelectricpolymer material. Materials for the electrodes are not particularlylimited, and include, for example, ITO, ZnO, IZO (registered trademark),conductive polymers and the like.

In particular, when an electrode is provided on a principal plane of thepiezoelectric polymer material, the electrode preferably hastransparency. In the present specification, when the electrode has aninternal haze of 20 or less (total light transmittance of 80% or more),the electrode is defined to have transparency.

The piezoelectric element formed from the piezoelectric polymer materialin accordance with the present embodiment may be applied to theabove-described various piezoelectric devices, such as the speakers andtouch panels. In particular, a piezoelectric element provided with anelectrode having transparency is suitably applied speakers, touchpanels, actuators and the like.

EXAMPLES

The embodiments of the present invention are further specificallydescribed below with reference to the Examples, but the embodiments arenot limited to the Examples.

First Embodiment Example 1-1

A polylactic acid-based resin (registered trademark LACEA, H-400, weightaverage molecular weight Mw: 200,000, manufactured by Mitsui Chemicals,Inc.) was melt-kneaded at 230° C. with an extruder and extruded from aT-die to form a original sheet with a thickness of 300 μm, and the sheetwas rolled with a cast roll having a surface temperature of 58° C.

Then, the original sheet was cut into a size of 7 cm in TD direction×13cm in MD direction and sandwiched between two plates made of aluminumeach having a size of 150 mm per side and a thickness of 0.15 mm, andheated at 90° C. for 2 minutes, and was subjected to preliminarilycrystallization to produce a crystallized original sheet (preliminarycrystallization step).

Then, two opposite ends of the crystallized original sheet were set tochucks of a tensile testing machine equipped with a constant-temperaturebath. The film was 7 cm in width, and the distance between the chuckswas 30 mm. Thereafter, the film surface temperature was increased fromroom temperature to a temperature of the constant-temperature bath,which was set at 80° C. Stretching was started at a stretching rate of100 min/min immediately after the temperature reached 80° C., and thefilm was uniaxially stretched at a stretching ratio of 4.1 times,thereby obtaining a uniaxially stretched film with a thickness of 0.05mm.

The uniaxially stretched film was sandwiched between two pieces ofsandpaper of #1500, and the three-layer laminate was further sandwichedbetween two aluminum plates with a thickness of 0.15 mm to form afive-layer laminate. The laminate was placed in an envelope-shapedvacuum pack made of a polyimide film with a thickness of 50 μm, and theinside thereof was degassed with a vacuum pump until it is in a vacuumstate. The vacuumed pack was inserted between an upper plate and a lowerplate of a heat press whose temperature was set at 150° C., with a gapof 1 mm. Thereafter, an annealing treatment was performed for 10minutes, thereby preparing a piezoelectric polymer material.

Examples 1-2 to 1-6, Comparative Example 1-1

Piezoelectric polymer materials of Examples 1-2 to 1-6 and ComparativeExample 1-1 were prepared in the same manner as the piezoelectricpolymer material of Example 1-1, except that the conditions forpreliminary crystallization and stretching were changed as shown inTable 1.

Example 1-7

A piezoelectric polymer material was prepared in the same manner asExample 1-1, except that the raw material for the sheet was changed fromthe polylactic acid-based resin (registered trademark: LACEA H-400,weight average molecular weight Mw: 200,000, manufactured by MitsuiChemicals, Inc.) to a mixture prepared by adding 0.1 parts by weight ofzinc phenylphosphonate (ECOPROMOTE, manufactured by Nissan ChemicalIndustries, Ltd.) to 100 parts by weight of H-400.

Example 1-8, Example 1-9 and Comparative Examples 1-2 to 1-7

Piezoelectric polymer materials of Example 1-8, Example 1-9 andComparative Examples 1-2 to 1-7 were prepared in the same manner as thepiezoelectric polymer material of Example 1-7, except that theconditions for preliminary crystallization and stretching and the amountof crystal nucleating agent were changed as shown in Table 1.

—Measurement of Amounts of L- and D-Isomers of Resin (Optically ActivePolymer)—

To a 50-mL conical flask, 1.0 g of the sample (piezoelectric polymermaterial) was weighed and placed, and 2.5 mL of IPA (isopropanol) and 5mL of a 5.0 mol/L sodium hydroxide solution were added.

The conical flask containing the sample solution was placed in a waterbath at a temperature of 40° C., and stirred for approximately 5 hoursuntil polylactic acid was completely hydrolyzed.

The sample solution was cooled to room temperature, and neutralized byadding 20 mL of 1.0 mol/L hydrochloric acid solution. Then, the conicalflask was stoppered and thoroughly stirred. HPLC sample solution 1 wasprepared by placing 1.0 mL of the sample solution in a 25-mL measuringflask and adjusting to 25 mL with a mobile phase.

Into an HPLC apparatus, 5 μL of the HPLC sample solution 1 was injected,and the peak areas of the D/L-isomers of polylactic acid were determinedunder the following HPLC conditions. The amounts of the L- and D-isomerswere calculated from the peak areas.

—HPLC Measurement Conditions—

Column

Optical resolution column, SUMICHIRAL OA5000, manufactured by SumikaChemical Analysis Service, Ltd.

Measuring Apparatus

Liquid chromatography manufactured by JASCO Corporation

Column Temperature

25° C.

Mobile Phase

1.0 mM-copper (II) sulfate buffer/IPA=98/2 (V/V)

Copper (II) sulfate/IPA/water=156.4 mg/20 mL/980 mL

Mobile Phase Flow Rate

1.0 ml/min

Detector

Ultraviolet detector (UV 254 nm)

<Molecular Weight Distribution>

The molecular weight distribution (Mw/Mn) of a resin (optically activepolymer), contained in each of the piezoelectric polymer materials ofthe Examples and the Comparative Examples, was measured by a GPCmeasuring method as described below.

—GPC Measuring Method—

Measuring Apparatus

GPC-100, manufactured by Waters Corporation

Column

SHODEX LF-804, manufactured by Showa Denko K.K.

Preparation of Sample

Each of the piezoelectric polymer materials of the Examples and theComparative Examples was dissolved in a solvent (chloroform) at 40° C.to prepare a sample solution with a concentration of 1 mg/ml.

Measurement Conditions

Into the column, 0.1 ml of the sample solution was introduced with asolvent (chloroform) at a temperature of 40° C. and a flow rate of 1ml/min, and the concentration of the sample in the sample solutionseparated in the column was measured by a differential refractometer.The weight-average molecular weight (Mw) of the resin was calculated byproducing a universal calibration curve with a polystyrene standardsample.

The results are shown in Table 1. In Table 1, “LA” represents LACEAH-400, and “EP” represents ECOPROMOTE. In addition, the amounts of theadditive are in part(s) by weight with respect to 100 parts by weight ofLACEA H-400.

TABLE 1(1) Preliminary Crystallized Crystallization Original Sheet SheetPhysical Properties of Resin Additive Heat Heating Degree of Thick-Optical Weight Temper- Time Crystallization ness Resin Chrality Mw Mw/MnPurity (%) Type Mw Parts (%) ature (min) (%) t (μm) Example 1-1 LA L200,000 2.87 98.5 — — — 90 2 17 300 Example 1-2 LA L 200,000 2.87 98.5 —— — 90 2 17 300 Example 1-3 LA L 200,000 2.87 98.5 — — — 90 2 17 300Example 1-4 LA L 200,000 2.87 98.5 — — — 90 2 17 300 Example 1-5 LA L200,000 2.87 98.5 — — — 75 0.2 5 150 Example 1-6 LA L 200,000 2.87 98.5— — — 75 0.14 4 230 Example 1-7 LA L 200,000 2.87 98.5 EP — 0.1 90 5 46300 Example 1-8 LA L 200,000 2.87 98.5 EP — 0.1 90 2 45 300 Example 1-9LA L 200,000 2.87 98.5 EP — 0.1 90 10 42 300 Comp. Example 1-1 LA L200,000 2.87 98.5 — — — 90 2 17 300 Comp. Example 1-2 LA L 200,000 2.8798.5 EP — 0.5 90 2 40 300 Comp. Example 1-3 LA L 200,000 2.87 98.5 EP —0.5 90 5 41 300 Comp. Example 1-4 LA L 200,000 2.87 98.5 EP — 0.5 90 3041 300 Comp. Example 1-5 LA L 200,000 2.87 98.5 EP — 1.0 90 2 41 300Comp. Example 1-6 LA L 200,000 2.87 98.5 EP — 1.0 90 5 40 300 Comp.Example 1-7 LA L 200,000 2.87 98.5 EP — 1.0 90 10 44 300

TABLE 1(2) Stretching Conditions Annealing MD TD Stretch ConditionsDirection Direction Rate Temperature Area Temperature Time Method RatioRatio (mm/min) (° C.) (mm²) (° C.) (sec) Cooling Conditions Example 1-1Uniaxial Stretching 4.1 1.0 100 80 7900 150 600 Rapid Cooling Example1-2 Uniaxial Stretching 4.1 1.0 500 80 7900 150 600 Rapid CoolingExample 1-3 Uniaxial Stretching 4.6 1.0 300 70 7900 150 600 RapidCooling Example 1-4 Uniaxial Stretching 4.6 1.0 200 80 7900 150 600Rapid Cooling Example 1-5 Uniaxial Stretching 3.3 1.0 70 500 mm 120  30Rapid Cooling in width Example 1-6 Uniaxial Stretching 3.5 1.5 70 500 mm120  30 Rapid Cooling in width Example 1-7 Uniaxial Stretching 6.9 1.0100 90 7900 150 600 Rapid Cooling Example 1-8 Uniaxial Stretching 6.01.0 500 70 7900 150 600 Rapid Cooling Example 1-9 Uniaxial Stretching8.3 1.0 100 90 7900 150 600 Rapid Cooling Comp. Example 1-1 UniaxialStretching 4.4 1.0 500 70 7900 150 600 Rapid Cooling Comp. Example 1-2Uniaxial Stretching 7.0 1.0 500 90 7900 150 600 Rapid Cooling Comp.Example 1-3 Uniaxial Stretching 6.0 1.0  30 80 7900 150 600 RapidCooling Comp. Example 1-4 Uniaxial Stretching 5.1 1.0  30 70 7900 150600 Rapid Cooling Comp. Example 1-5 Uniaxial Stretching 7.7 1.0 100 907900 150 600 Rapid Cooling Comp. Example 1-6 Uniaxial Stretching 7.5 1.0100 90 7900 150 600 Rapid Cooling Comp. Example 1-7 Uniaxial Stretching6.5 1.0 100 80 7900 150 600 Rapid Cooling

<Measurement and Evaluation of Physical Properties>

The glass transition temperature Tg, melting point Tm, crystallinity,specific heat capacity Cp, thickness, haze, piezoelectric constant, MORcand dimensional stability of the piezoelectric polymer materials ofExamples 1-1 to 1-9 and Comparative Examples 1-1 to 1-7, which wereobtained in the process as described above, were measured. The resultsare shown in Table 2. In Table 2, the internal haze described as “0.0”is a value obtained by rounding to one decimal place.

Specifically, the physical properties were measured by the methods asdescribed below.

[Glass Transition Temperature Tg, Melting Point Tm and Crystallinity]

Each of the piezoelectric polymer material of the Examples and theComparative Examples was precisely weighed to 10 mg, and was measuredwith a differential scanning calorimeter (DSC-1 manufactured byPerkinElmer, Inc.) at a rate of temperature increase of 10° C./min,thereby obtaining a melt endothermic curve. The melting point Tm, theglass transition temperature Tg, the specific heat capacity Cp and thecrystallinity were obtained from the obtained melt endothermic curve.

[Specific Heat Capacity Cp]

During the measurement with the above-described differential scanningcalorimeter, the quantity of heat that is necessary for increasing thetemperature by 1° C. per gram was measured. The measurement wasperformed under the same conditions as the measurement of Tg and Tm.

[Dimensional Stability]

The stretched film was cut into a size of 30 mm in a stretchingdirection (MD direction) and 6 mm in a direction perpendicular to thestretching direction (TD direction), thereby obtaining a rectangularfilm of 30 mm×6 mm. The rectangular film was sandwiched between twopieces of sandpaper of #1500, and the three-layer laminate was furthersandwiched between two aluminum plates with a thickness of 0.15 mm,thereby preparing a five-layer laminate. The laminate was placed in anenvelope-shaped vacuum pack made of a polyimide film with a thickness of50 μm, and the inside thereof was degassed with a vacuum pump until itwas in a vacuum state. The vacuumed polyimide envelope was insertedbetween an upper plate and a lower plate of a heat press, whosetemperature was set at 150° C., with a gap of 1 mm. Then, an annealingtreatment was performed for 10 minutes, and the dimensional stabilitywas evaluated based on an absolute value of a rate of change in the filmlength (%) before and after the annealing.

[Internal Haze]

In the present specification, “Haze” or “transmission haze” refers to aninternal haze of the piezoelectric polymer material according to thepresent invention, and is measured by an ordinary method. Specifically,the internal haze value of each of the piezoelectric polymer materialsof the Examples and the Comparative Examples was measured as an opticaltransparency in a thickness direction with an apparatus described below,under the measurement conditions described below. The internal haze(hereinafter, also referred to as internal haze (H1)) of thepiezoelectric polymer material according to the present invention wascalculated from a haze (H2), which was measured by placing silicone oil(SHIN-ETSU SILICONE (trademark), manufactured by Shin-Etsu Chemical Co.,Ltd., model number: KF96-100CS) between two glass place, and a haze(H3), which was measured by sandwiching a film having a surfaceuniformly wet with silicone oil with two glass plates, in accordancewith the following expression.

Internal haze(H1)=Haze(H3)−Haze(H2)

In order to calculate the internal haze (H1) of each of thepiezoelectric polymer materials of the Examples and the ComparativeExamples, the haze (H2) and the haze (H3) were obtained by measuring theoptical transparency in a thickness direction with the followingapparatus under the following conditions.

Measuring apparatus: HAZE METER TC-HIIIDPK, manufactured by TokyoDenshoku Co., Ltd.

Sample size: 30 mm in width×30 mm in length, 0.05 mm in thickness

Measurement conditions: compliant with JIS-K7105

Measurement temperature: room temperature (25° C.)

[Piezoelectric Constant d₁₄ (Measured by Displacement Method)]

A test piece of 40 mm×40 mm having an Ag conductive layer on both faceswas cut into a size of 32 mm in a direction of 45° with respect to astretching direction (MD direction) of the piezoelectric polymermaterial and 5 mm in a direction perpendicular to the direction of 45°to a stretching direction, thereby preparing a rectangular film of 32mm×5 mm. This was used as a sample for measurement of a piezoelectricconstant.

An alternating voltage of 10 Hz and 300 Vpp was applied to the resultantfilm, and the difference in distance between a maximal value and aminimum value of displacement of the film was measured by a laserspectral-interference displacement meter (SI-1000, manufactured byKeyence Corporation).

The value obtained by dividing the measured amount of displacement(mp-p) by a reference length of the film (30 mm) was used as an amountof deformation. Then, the amount of deformation was divided by anelectric field intensity ((applied voltage (V))/(film thickness))applied to the film. The result was squared, and was used as apiezoelectric constant d₁₄ (pm/V).

[Standardized Molecular Orientation MORc]

The standardized molecular orientation MORc was measured by a microwavetype molecular orientation meter (MOA-6000, manufactured by OjiScientific Instruments Co., Ltd.) with a reference thickness tc of 50μm.

TABLE 2(1) Tg Cp Tm Crystallinity Thickness MORc Internal Haze (° C.)(J/g° C.) (° C.) (%) (mm) at 50 μm (%) Example 1-1 65.5 0.326 166.5 42.50.114 7.62 0.3 Example 1-2 70.9 0.168 163.0 45.0 0.126 7.14 0.1 Example1-3 76.8 0.215 168.7 46.6 0.118 7.21 0.1 Example 1-4 76.4 0.357 169.048.0 0.102 7.02 4.0 Example 1-5 — — 169.5 41.9 0.064 6.10 0.15 Example1-6 69.8 — 171.0 41.9 0.03 4.03 0.0 Example 1-7 78.0 0.101 170.3 50.30.08 8.32 11.9 Example 1-8 83.0 0.103 170.2 52.4 0.05 8.29 24.6 Example1-9 72.4 0.284 170.2 48.9 0.042 7.06 39.9 Comp. Example 1-1 57.0 0.254170.3 47.7 0.068 7.43 90.5 Comp. Example 1-2 69.7 0.066 170.5 48.9 0.0488.64 51.8 Comp. Example 1-3 69.0 0.220 169.8 48.8 0.063 8.34 92.4 Comp.Example 1-4 69.7 0.084 168.9 50.8 0.089 7.80 91.1 Comp. Example 1-5 70.70.038 170.9 51.5 0.047 7.55 87.3 Comp. Example 1-6 71.0 0.030 170.4 51.30.035 9.00 87.7 Comp. Example 1-7 69.6 0.104 169.7 53.7 0.049 7.61 93.5

TABLE 2(2) Piezoelectric Piezoelectric Constant Constant (resonance(displacement MORc Length after Ratio of Change method) method) xAnnealing in Dimension Thickness Width (pC/N) (pm/V) Crystallinity (mm)(%) (mm) (mm) Example 1-1 10.6 8.6 324 28.98 3.40 0.095 5.99 Example 1-210.5 8.4 321 29.43 1.90 0.125 5.79 Example 1-3 10.5 8.3 336 28.77 4.100.104 5.87 Example 1-4 10.2 8.1 337 27.99 6.70 0.114 5.94 Example 1-59.5 6.93 255.6 29.4 1.90 — — Example 1-6 6.3 4.18 168.9 28.5 5.00 — —Example 1-7 11.6 9.5 419 28.85 3.83 0.066 5.91 Example 1-8 11.9 9.9 43428.69 4.37 0.135 5.58 Example 1-9 10.5 8.4 345 26.81 10.63 0.073 5.71Comp. Example 1-1 10.8 8.7 354 29.19 2.70 0.121 6.00 Comp. Example 1-210.4 8.3 423 24.92 16.93 0.116 6.42 Comp. Example 1-3 9.9 7.7 407 25.0416.53 0.146 6.43 Comp. Example 1-4 9.1 6.8 396 25.68 14.40 0.078 6.29Comp. Example 1-5 10.7 8.6 388 26.67 11.10 0.087 6.21 Comp. Example 1-610.6 8.4 462 27.11 9.63 0.069 5.85 Comp. Example 1-7 10.9 8.8 409 27.627.93 0.068 6.08

Example 1-10

—Production of Film A11 Prior to Stretching—

Approximately 4 g of pellets of a resin having optical activity(polylactic acid-based resin, registered trademark: LACEA H-400, weightaverage molecular weight Mw: 200,000, manufactured by Mitsui Chemicals,Inc.) were weighed and placed between two SUS plates of 250 mm per sideand a thickness of 5 mm, via an aluminum plate spacer of 0.15 mm inthickness and 250 mm per side, the spacer having a disk-shaped hole witha diameter of 150 mm. The assembly was pressed by hot plates whosetemperature was set at 230° C. in a heat press (trademark: MINI TESTPRESS, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 5 MPa for 3minutes (hereinafter, the treatment is referred to as “heat presstreatment”).

After the heat press treatment, the temperature was rapidly decreased toroom temperature by an air-cooling fan while applying a pressure,whereby a disk-shaped unstretched film A11 having a diameter of 150 mmand a thickness of 150 μm was obtained.

Specific means for obtaining the disk-shaped sheet of polylactic acid isexplained with reference to the drawings.

FIG. 1 illustrates a schematic view (perspective view) of a heat presstreatment in which the spacer 4 is sandwiched between the two SUS plates2. FIG. 2 illustrates a schematic view (side cross-sectional view) of aheat and pressure-application apparatus (heat press machine) 10 in astate of pressing, with hot plates, the polylactic acid pellets 6 thatare sandwiched between the two SUS plates 2.

In FIG. 1, the spacer 4 is an aluminum plate of 0.15 mm in thickness and250 mm per side, having a disk-shaped hole with a diameter of 150 mm inthe center. The SUS plates 2 are made of stainless steel and have a sizeof 250 mm per side and 5 mm in thickness.

The polylactic acid pellets 6 were placed in the hole of the spacer 4,and were sandwiched with the SUS plates 2.

The SUS plates 2, between which the spacer 4 and the polylactic acidpellets 6 were sandwiched, were further sandwiched between the hotplates 8 and pressed by the heat press machine 10, as illustrated inFIG. 2.

—Uniaxial Stretching Treatment (1)—

In order to perform uniaxial stretching, a rectangular film A12 with awidth of 100 mm and a length of 50 mm was cut from the heat-pressedunstretched film A11.

The film was set in POLYMER FILM X AND Y-AXIS STRETCHING SYSTEM SS-60,manufactured by Shibayama Scientific Co., Ltd.), and portions of 1 cmfrom the edges in a 100-mm longer direction of the film A12 were fixedwith chucks, in such a manner that the shape of the film before thestretching was substantially 100 mm in width and 30 mm in length. Thetemperature inside the system was set at 70° C., and immediately afterthe temperature inside the system and the surface temperature of thefilm reached 70° C., the stretching operation was performed.

The film A12 was stretched under the conditions of a temperature insidethe system of 70° C., a stretching ratio of 5 times, and a stretchingrate of 30 mm/min.

—Annealing Treatment (1)—

In order to perform an annealing treatment, the temperature inside theapparatus was set at 150° C. while chucking the film A12 in theapparatus, and the temperature was maintained at 150° C. Thereafter, thefilm was sprayed with a cooling spray (134aQREI, manufactured bySunhayato Corp.) to cool to the glass transition temperature or lower.

A film A13, which had been annealed and stretched at a ratio of 5 timesand had the size of 50 mm in width, 150 mm in length, 0.06 mm inthickness and 7,200 mm² in area, was thus obtained.

—Hydrolysis Treatment (1)—

In order to perform hydrolysis, a rectangular film A14 of 45 mm in widthand 90 mm in length was cut from the film A13 that had been subjected tothe first annealing treatment.

The film was set to a fixation instrument for uniaxial stretching.Portions of 1 cm from the edges in a 90-mm longer direction of the filmA14 were fixed with chucks, in such a manner that the size of the filmbefore being stretched was substantially 45 mm in width and 70 mm inlength. The film was then subjected to a hydrolysis treatment byimmersing in warm water at 90° C. for 1 hour together with the fixationinstrument.

—Uniaxial Stretching Treatment (2)—

Subsequently, the second uniaxial stretching treatment was performed inwarm water at 90° C. at a stretch ratio of 1.05 times and a stretchingrate of 30 mm/min.

—Annealing Treatment (2)—

In order to perform an annealing treatment, the uniaxially stretchedfilm was placed in a hot air dryer set at 150° C., together with thefixation instrument, and was left to stand for 1 hour. Thereafter, thefilm was cooled to the glass transition temperature or lower with acooling spray (134aQREI, manufactured by Sunhayato Corp.)

The uniaxial stretching treatment at a stretching ratio of 1.05 timesand the annealing treatment were conducted four times, respectively,thereby producing a piezoelectric polymer material 1-10 of Example 1-10that had been stretched at a stretch ratio of 6.1 times.

Example 1-11

A rectangular film was obtained in the same manner as Example 1-10,except that the film was cut from a film that had been annealed andstretched at a stretching ratio of 8 times, and the film was set to afixation instrument for uniaxial stretching.

A piezoelectric polymer material 1-11 of Example 1-11, which wasstretched at a stretching ratio of 8.4 times, was produced in the samemanner as Example 1-10, except that the film was immersed in warm waterat 90° C. for 4 hours, instead of immersing in warm water for 1 hour.

<Measurement and Evaluation of Physical Properties>

The weight average molecular weight, melting point Tm, crystallinity,thickness, haze (internal haze), piezoelectric constant and MORc of thepiezoelectric polymer materials of Examples 1-10 and 1-11 were measured.The results are shown in Table 4.

Specifically, they were measured as described below.

<Weight Average Molecular Weight>

The weight average molecular weight before the hydrolysis treatment(Mw1) and the weight average molecular weight after the final annealingtreatment (Mw2) in the Examples and the Comparative Examples weremeasured by a GPC measuring method as described below. In addition, amolecular weight remaining rate was defined and calculated by thefollowing Expression (1):

Molecular weight remaining rate=[Mw2/Mw1]×100(%)  Expression (1)

—GPC Measuring Method—

Measuring Apparatus

GPC-100, manufactured by Waters Corporation

Column

SHODEX LF-804, manufactured by Showa Denko K.K.

Preparation of Sample

Each of the piezoelectric polymer materials of the Examples and theComparative Examples was dissolved in a solvent (chloroform) at 25° C.to prepare a sample solution with a concentration of 1 mg/ml.

Measurement Conditions

Into the column, 0.1 ml of the sample solution was introduced with asolvent (chloroform) at a temperature of 40° C. and a flow rate of 1ml/min, and the concentration of the sample in the sample solutionseparated in the column was measured by a differential refractometer.The weight-average molecular weight (Mw) of the resin was calculated byproducing a universal calibration curve with a polystyrene standardsample.

The results are show in Table 4.

[Melting Point Tm and Crystallinity]

Each of the piezoelectric polymer materials of the Examples and theComparative Examples was precisely weighed to 5 mg, and was measuredwith a differential scanning calorimeter (DSC-1 manufactured byPerkinElmer, Inc.) at a rate of temperature increase of 10° C./min,thereby obtaining a melt endothermic curve. The melting point Tm, theglass transition temperature Tg and the crystallinity were obtained fromthe obtained melt endothermic curve.

[Haze (Internal Haze)]

In the present specification, “Haze” or “transmission haze” refers to aninternal haze of the piezoelectric polymer material according to thepresent invention, and is measured by an ordinary method. Specifically,the internal haze value of each of the piezoelectric polymer materialsof the Examples and the Comparative Examples was measured as an opticaltransparency in a thickness direction with an apparatus described below,under the measurement conditions described below. The internal haze(hereinafter, also referred to as internal haze (H1)) of thepiezoelectric polymer material according to the present invention wascalculated from a haze (H2), which was measured by placing silicone oil(SHIN-ETSU SILICONE (trademark), manufactured by Shin-Etsu Chemical Co.,Ltd., model number: KF96-100CS) between two glass plates, and a haze(H3), which was measured by sandwiching a film having a surfaceuniformly wet with silicone oil with two glass plates, in accordancewith the following expression.

Internal haze(H1)=Haze(H3)−Haze(H2)

In order to calculate the internal haze (H1) of each of thepiezoelectric polymer materials of the Examples and the ComparativeExamples, the haze (H2) and the haze (H3) were obtained by measuring theoptical transparency in a thickness direction with the followingapparatus under the following conditions.

Measuring apparatus: HAZE METER TC-HIIIDPK, manufactured by TokyoDenshoku Co., Ltd.

Sample size: 30 mm in width×30 mm in length, 0.05 mm in thickness

Measurement conditions: compliant with JIS-K7105

Measurement temperature: room temperature (25° C.)

[Piezoelectric Constant d₁₄ (Measured by Displacement Method)]

A test piece was prepared by cutting each of the piezoelectric polymermaterial of Examples 1-10 and 1-11 into a size of 1 cm in length and 3mm in width.

The complex piezoelectric modulus d₁₄ of the obtained test piece wasmeasured with RHEOLOGRAPH SOLID S-1, manufactured by Toyo SeikiSeisaku-sho, Ltd. at a frequency of 10 Hz at room temperature. Thecomplex piezoelectric modulus d₁₄ was calculated by the expressiond₁₄=d₁₄′−d₁₄″. The measurement of piezoelectric constant was carried outfive times, and an average value of d₁₄′ is shown in Table 4 as thepiezoelectric modulus.

The shear strain during the measurement of piezoelectric constant wasset at 0.05%.

[Standardized Molecular Orientation MORc]

The standardized molecular orientation MORc was measured by a microwavetype molecular orientation meter (MOA-6000, manufactured by OjiScientific Instruments Co., Ltd.) with a reference thickness tc of 50μm.

TABLE 3 Uniaxial Hydrolysis/Stretching Conditions Stretching AnnealingAnneal- Conditions (1) Conditions (1) Stretching ing Anneal- NumberTemper- Temper- Temper- Temper- Temper- ing of Total ature ature TimeTreatment ature Time Stretching ature ature Time Repe- Stretching Ratio(° C.) (° C.) (H) Apparatus (° C.) (H) Ratio (° C.) (° C.) (H) titionsRatio Example 1-10 5.0 70 150 1 Water 90 1 1.05 90 150 1 4 6.1 BathExample 1-11 8.0 70 150 1 Water 90 4 1.05 90 150 1 4 8.4 Bath

TABLE 4 Weight Average Molecular Weight Molecular Mw1 Mw2 Weight MORcPiezoelectric Before After Final Remaining Tm Crystallinity ThicknessMORc x Internal Haze Constant d₁₄ Hydrolysis Annealing Rate (° C.) (%)(mm) at 50 μm Crystallinity (%) (pm/V) Example 1-10 216,000 122,000 56.4166.3 60.2 0.057 6.9 415.4 0.9  9.5 Example 1-11 207,000 158,000 76.3167   62.7 0.035 7.8 489.1 0.5 11.8

Second Embodiment Comparative Example 2-1

—Production of Blend—

Pellets of polylactic acid H-400 (registered trademark: LACEA, weightaverage molecular weight Mw: 240,000, manufactured by Mitsui ChemicalsInc.) were used as a polylactic acid-based polymer, and pellets ofpolyvinylidene fluoride (weight average molecular weight Mw: 530,000,manufactured by Sigma-Aldrich Corporation) were used as polyvinylidenefluoride.

Polylactic acid H-400 (90 parts by mass) and polyvinylidene fluoride (10parts by mass) were melt-kneaded for 10 minutes at a mixer revolutionspeed of 50 rpm at 210° C. with a melt-kneading machine (manufactured byToyo Seiki Seisaku-sho, Ltd.; LABO PLASTOMILL MIXER), thereby obtaininga blend of polylactic acid and polyvinylidene fluoride (blend 101).

—Production of Unstretched Film—

4 g of the blend 1 were weighed and sandwiched between two SUS plates of250 mm per side and 5 mm in thickness via a spacer made of an aluminumplate of 0.15 mm in thickness and 250 mm per side, having a disk-shapedhole with a diameter of 150 mm in the center, and a pressure of SMPa wasapplied thereto for 3 minutes with hot plates whose temperature was setat 210° C. in a heat press (trademark: MINI TEST PRESS, manufactured byToyo Seiki Seisaku-sho, Ltd.) (the treatment is referred to as “heatpress treatment”).

After the heat press treatment, the temperature was rapidly returned toroom temperature with an air-cooling fan while applying pressure,thereby obtaining a disk-shaped unstretched film A1 having a diameter of150 mm and a thickness of 150 μm.

—Uniaxial Stretching—

In order to perform uniaxial stretching, a rectangular film A2 with awidth of 100 mm and a length of 50 mm was cut from the heat-pressedunstretched film A1.

The film A2 was set in POLYMER FILM X AND Y-AXIS STRETCHING SYSTEMSS-60, manufactured by Shibayama Scientific Co., Ltd., and thetemperature inside the system was set at 70° C. Immediately after thetemperature reached 70° C., the stretching operation was performed.

The film A2 was stretched at a temperature inside the system (stretchingtemperature) of 70° C., a stretching ratio of 6 times, and a stretchingrate of 30 mm/min, whereby a film A3 was obtained.

—Annealing Treatment—

In order to perform an annealing treatment, the temperature inside thesystem was set at 150° C., while the film A3 was kept in the stretchingsystem, and the temperature was maintained at 150° C. for 10 minutes.Thereafter, the film was sprayed with a cooling spray (134aQREI,manufactured by Sunhayato Corp.) to cool to the glass transitiontemperature or lower.

A piezoelectric polymer material 101 of Comparative Example 2-1 was thusproduced.

Example 2-1 to Example 2-11 and Comparative Example 2-2 to ComparativeExample 2-4

Blends 1-8 and 102-104 were produced in the same manner as the blend 101of Comparative Example 2-1, except that polylactic acid (PLA) andpolyvinylidene fluoride (PVDF) were changed to those shown in Table 5.

Subsequently, piezoelectric polymer materials 1-11 and 102-104 ofExample 2-1 to Example 2-11 and Comparative Example 2-2 to ComparativeExample 2-4 were produced in the same manner as the piezoelectricpolymer material 101 of Comparative Example 2-1, except that the blendsshown in Table 5 were used and the stretching conditions were changed tothose shown in Table 5.

In Table 5, “H-400 crosslinked” in the column “PLA” refers to a polymerobtained by mixing 99.6 parts by mass of polylactic acid H-400(registered trademark LACEA; weight average molecular weight Mw:240,000, manufactured by Mitsui Chemicals Inc.) with 0.4 parts by massof a crosslinking agent (manufactured by NOF Corporation; organicperoxide PH25B) under 210° C., and is a compound containing a repeatingunit represented by Formula (1) as a main chain.

The melting points Tm of the polyvinylidene fluorides used in theExamples were as follows:

-   -   PVDF (Mw: 530,000) . . . Tm: 171° C.    -   PVDF (Mw: 280,000) . . . Tm: 170° C.    -   PVDF (Mw: 180,000) . . . Tm: 172° C.

Comparative Example 2-5

A piezoelectric polymer material 105 of Comparative Example 2-1 wasproduced in the same manner as the piezoelectric polymer material 101 inComparative Example 2-1, except that only polylactic acid H-400(registered trademark: LACEA, manufactured by Mitsui Chemicals Inc.,weight average molecular weight Mw: 200,000) was used instead of theblend 101.

Comparative Example 2-6

A piezoelectric polymer material 106 of Comparative Example 2-6 wasproduced in the same manner as the piezoelectric polymer material 101 inComparative Example 2-1, except that only polyvinylidene fluoride(weight average molecular weight Mw: 180,000, manufactured bySigma-Aldrich Corporation) was used instead of the blend 101.

Comparative Example 2-7

A blend 105 was produced in the same manner as the blend 7 for thepiezoelectric polymer material 9 of Example 2-9, except thatacetylcellulose (number average molecular weight Mn: 30,000,manufactured by Sigma-Aldrich Corporation) was used instead ofpolyvinylidene fluoride (weight average molecular weight Mw: 180,000,manufactured by Sigma-Aldrich Corporation).

Subsequently, a piezoelectric polymer material 107 of ComparativeExample 2-7 was produced in the same manner as the piezoelectric polymermaterial 101 of Comparative Example 2-1, except that the blend 105 wasused instead of the blend 101.

In Table 5, “0.50%*” described in the column “mass ratio PLA/PVDF”indicates a mass ratio of PLA/acetylcellulose, and “99.5:0.5*” describedin the column “mass ratio PLA:PVDF” indicates a mass ratio of PLA:acetylcellulose.

<Measurement and Evaluation of Physical Properties>

The glass transition temperature Tg, melting point Tm, crystallinity,piezoelectric constant, standardized molecular orientation MORc anddimensional change rate of the piezoelectric polymer materials 1-11 ofExamples 2-1 to 2-11 and the piezoelectric polymer materials 101-107 ofComparative Examples 2-1 to 2-7, obtained in the processes as describedabove, were measured. The results are shown in Table 6.

Specifically, the measurements were conducted in accordance with thefollowing processes.

[Glass Transition Temperature Tg, Melting Point Tm and Crystallinity]

Each of the piezoelectric polymer materials of the Examples and theComparative Examples was precisely weighed to 10 mg, and a meltendothermic curve was obtained therefrom with a differential scanningcalorimeter (DSC-1, manufactured by PerkinElmer, Inc.) at a temperatureincrease rate of 10° C./min. The melting point Tm, the glass transitiontemperature Tg and the crystallinity were obtained from the obtainedmelt endothermic curve.

[Transparency (Internal Haze)]

Transparency of the piezoelectric polymer materials of Examples 2-1 to2-11 and the piezoelectric polymer materials of Comparative Examples 2-1to 2-7 was evaluated by measuring a haze value (internal hazes) of thepiezoelectric polymer materials. The internal haze (hereinafter, alsoreferred to as internal haze (H1)) of the piezoelectric polymer materialaccording to the present invention was calculated from a haze (H2),which was measured by placing silicone oil (SHIN-ETSU SILICONE(trademark), manufactured by Shin-Etsu Chemical Co., Ltd., model number:KF96-100CS) between two glass place, and a haze (H3), which was measuredby sandwiching a film having a surface uniformly wet with silicone oilwith two glass plates, in accordance with the following expression.

Internal haze(H1)=Haze(H3)−Haze(H2)

In order to calculate the internal haze (H1) of each of thepiezoelectric polymer materials of the Examples and the ComparativeExamples, the haze (H2) and the haze (H3) were obtained by measuring theoptical transparency in a thickness direction with the followingapparatus under the following conditions.

Measuring apparatus: HAZE METER TC-HIIIDPK, manufactured by TokyoDenshoku Co., Ltd.

Sample size: 30 mm in width×30 mm in length, 0.05 mm in thickness

Measurement conditions: compliant with JIS-K7105

Measurement temperature: room temperature (25° C.)

Evaluation was carried out in accordance with the following evaluationcriteria based on the degree of the obtained haze value (internal haze).

—Evaluation Criteria—

A: Haze value (internal haze) is 6% or less.

B: Haze value (internal haze) is from more than 6% to 40%.

C: Haze value (internal haze) is more than 40%.

[Piezoelectric Constant (Measured by Resonance Method)]

Each of the piezoelectric polymer materials of the Examples and theComparative Examples was cut into a size of 32 mm in a stretchingdirection (MD direction) and 30 mm in a direction perpendicular to thestretching direction (TD direction), thereby preparing a rectangulartest piece.

The resultant test piece was set on a test bench of QUICK COATER SC-701,manufactured by Sanyu Electron Co., Ltd., and the inside of a coaterchamber was vacuumed (for example, 10⁻³ Pa or less) with a rotary pump.

Thereafter, one face of the test piece was subjected to sputtering for 3minutes with Au (gold) target at a sputtering current of 4 mA.Subsequently, the other face of the test piece was subjected tosputtering under the same conditions for 3 minutes, thereby forming anAu conductive layer on both faces of the test piece.

The test piece of 32 mm×30 mm, having Au conductive layers on bothsides, was cut into a size of 10 mm in a stretching direction (MDdirection) of the piezoelectric polymer material and 9 mm in a directionperpendicular to the stretching direction (TD direction). This was usedas a sample for a resonance/anti-resonance method measurement.

A resonance curve of impedance that appears in a band region of from 50kHz to 100 kHz was measured with an impedance analyzer HP4194A,manufactured by Yokogawa-Hewlett-Packard Company. From the obtainedresonance curve of impedance and a relative dielectric constant Er, apiezoelectric constant d₁₄ was calculated by a method described in Jpn.J. Appl. Phys. Vol. 37 (1998) pp. 3374-3376, part 1, No. 6A, June 1998.

The obtained piezoelectric constant was used as the piezoelectricconstant of the piezoelectric polymer material.

The relative dielectric constant ∈_(r) was calculated by the Expression(A) as described above from a capacitance C [F] measured with an LCRmeter HP4284A, manufactured by Hewlett-Packard Company, for the samplefor resonance/anti-resonance method measurement.

[Dimensional Stability]

The stretched film was cut into a size of 30 mm in a stretchingdirection (MD direction) and 6 mm in a direction perpendicular to thestretching direction (TD direction), thereby obtaining a rectangularfilm of 30 mm×6 mm. The rectangular film was sandwiched between twopieces of sandpaper of #1500, and the three-layer laminate was furthersandwiched between two aluminum plates with a thickness of 0.15 mm,thereby preparing a five-layer laminate. The laminate was placed in anenvelope-shaped vacuum pack made of a polyimide film with a thickness of50 μm, and the inside thereof was degassed with a vacuum pump until itwas in a vacuum state. The vacuumed polyimide envelope was insertedbetween an upper plate and a lower plate of a heat press, whosetemperature was set at 150° C., with a gap of 1 mm. Then, an annealingtreatment was performed for 10 minutes, and the dimensional stabilitywas evaluated based on an absolute value of a rate of change in the filmlength (%) before and after the annealing.

[Standardized Molecular Orientation MORc]

The standardized molecular orientation MORc was measured by a microwavetype molecular orientation meter (MOA-6000, manufactured by OjiScientific Instruments Co., Ltd.) with a reference thickness tc of 50μm.

TABLE 5(1) Composition and Conditions of Production of PiezoelectricPolymer Material Polymer 1 Polymer 2 Mass Ratio Crystallized PLA TypeType Mw PVDF/PLA PLA:PVDF Blend No. Original Sheet Example 2-1 H-400PVDF 530,000 2.56% 97.5:2.5 1 150 Example 2-2 H-400 PVDF 530,000 1.01%99:1 2 150 Example 2-3 H-400 PVDF 280,000 2.56% 97.5:2.5 3 150 Example2-4 H-400 PVDF 280,000 1.01% 99:1 4 150 Example 2-5 H-400 PVDF 280,0001.01% 99:1 4 150 Example 2-6 H-400 PVDF 280,000 2.56% 97.5:2.5 5 150Example 2-7 H-400 PVDF 180,000 1.01% 99:1 6 150 Example 2-8 H-400 PVDF180,000 1.01% 99:1 6 150 Example 2-9 H-400 PVDF 180,000 0.50% 99.5:0.5 7150 Example 2-10 H-400 Crosslinked PVDF 180,000 1.01% 99:1 8 150 Example2-11 H-400 Crosslinked PVDF 180,000 1.01% 99:1 8 150 Comp. Example 2-1H-400 PVDF 530,000 11.10%   90:10 101 150 Comp. Example 2-2 H-400 PVDF530,000 5.26% 95:5 102 150 Comp. Example 2-3 H-400 PVDF 280,000 5.26%95:5 103 150 Comp. Example 2-4 H-400 PVDF 180,000 5.26% 95:5 104 150Comp. Example 2-5 H-400 Not used — 0.00% 100:0  — 150 Comp. Example 2-6Not used PVDF 180,000 —   1:100 — 150 Comp. Example 2-7 H-400 Cellulose—  0.50%*  99.5:05* 105 150

TABLE 5(2) Composition and Conditions of Production of PiezoelectricPolymer Material Conditions for Stretching Conditions Temper- Stretchingfor Annealing ature Rate Area Temperature Time Conditions for Method (°C.) Ratio (mm/min) (mm²) (° C.) (sec) Cooling Example 2-1 UniaxialStretching 70° C. 6 times 30 7900 150 600 Rapid Cooling Example 2-2Uniaxial Stretching 70° C. 6 times 30 7900 150 600 Rapid Cooling Example2-3 Uniaxial Stretching 70° C. 6 times 30 7900 150 600 Rapid CoolingExample 2-4 Uniaxial Stretching 70° C. 6 times 30 7900 150 600 RapidCooling Example 2-5 Uniaxial Stretching 80° C. 6 times 30 7900 150 600Rapid Cooling Example 2-6 Uniaxial Stretching 70° C. 6 times 30 7900 150600 Rapid Cooling Example 2-7 Uniaxial Stretching 70° C. 6 times 30 7900150 600 Rapid Cooling Example 2-8 Uniaxial Stretching 80° C. 6 times 307900 150 600 Rapid Cooling Example 2-9 Uniaxial Stretching 70° C. 6times 30 7900 150 600 Rapid Cooling Example 2-10 Uniaxial Stretching 70°C. 6 times 30 7900 150 600 Rapid Cooling Example 2-11 UniaxialStretching 75° C. 6 times 30 7900 150 600 Rapid Cooling Comp. Example2-1 Uniaxial Stretching 70° C. 6 times 30 7900 150 600 Rapid CoolingComp. Example 2-2 Uniaxial Stretching 70° C. 6 times 30 7900 150 600Rapid Cooling Comp. Example 2-3 Uniaxial Stretching 70° C. 6 times 307900 150 600 Rapid Cooling Comp. Example 2-4 Uniaxial Stretching 70° C.6 times 30 7900 150 600 Rapid Cooling Comp. Example 2-5 UniaxialStretching 70° C. 6 times 30 7900 150 600 Rapid Cooling Comp. Example2-6 Uniaxial Stretching 160° C.  6 times 30 7900 150 600 Rapid CoolingComp. Example 2-7 Uniaxial Stretching 70° C. 6 times 30 7900 150 600Rapid Cooling

TABLE 6(1) Evaluation Tg Tm Crystallinity MORc Internal Haze (° C.) (°C.) (%) Transparency at 50 μm (%) Example 2-1 69.6 166.5 47.2 B 5.4Example 2-2 69.3 167.1 45.8 A 5.3 0.9 Example 2-3 68.3 167.3 43.9 BExample 2-4 70.5 168.8 48.0 A 5.4 0.9 Example 2-5 69.5 170.6 54.1 A 5.73.4 Example 2-6 68.0 169.5 44.0 B 5.3 Example 2-7 70.6 170.3 47.5 A 5.40.9 Example 2-8 69.7 170.1 50.6 A 5.5 0.9 Example 2-9 66.3 169.9 55.6 A5.7 0.9 Example 2-10 67.5 167.6 50.9 A 6.4 0.7 Example 2-11 69.5 168.855.2 A 5.6 0.7 Comp. Example 2-1 62.5 167.3 45.2 C 5.3 Comp. Example 2-269.1 167.6 48.2 C 5.4 Comp. Example 2-3 68.3 167.6 42.2 C Comp. Example2-4 71.4 169.3 47.9 C 5.4 Comp. Example 2-5 57.0 157.8 64.0 A 6.0 0.3Comp. Example 2-6 — 171.8 — C Comp. Example 2-7 66.0 168.0 49.5 C 5.5

TABLE 6(2) Evaluation Piezoelectric Constant Piezoelectric ConstantLength after Ratio of Change in (resonance method) (displacement method)MORc × Annealing Dimension (pC/N) (pmN) Crystallinity (mm) (%) Example2-1 11.0 8.10 254.9 2.3 Example 2-2 12.0 9.20 244.6 37 3.2 Example 2-311.0 8.10 2.1 Example 2-4 11.0 8.10 260.5 4.2 Example 2-5 11.0 8.10310.5 35.7 3.5 Example 2-6 11.0 8.10 232.9 2.7 Example 2-7 12.0 9.20 2573.3 Example 2-8 11.0 8.10 279.1 2.2 Example 2-9 13.0 10.30 318.4 1.3Example 2-10 12.0 9.20 327.9 50 2.2 Example 2-11 12.0 9.20 307.9 3.7 1.8Comp. Example 2-1 10.0 7.00 241.1 2.2 Comp. Example 2-2 11.0 8.10 2621.9 Comp. Example 2-3 10.0 7.00 2.5 Comp. Example 2-4 11.0 8.10 259.82.1 Comp. Example 2-5 9.0 5.90 382.1 1.8 Comp. Example 2-6 0 2.5 Comp.Example 2-7 10.0 7.00 271.2 2.3

All of the piezoelectric polymer materials of the Examples in Table 6exhibited excellent transparency and a large piezoelectric constant asmeasured by a resonance method of 11 pC/N or more.

All publications, patent applications, and technical standards mentionedin this specification are herein incorporated by reference to the sameextent as if each individual publication, patent application, ortechnical standard was specifically and individually indicated to beincorporated by reference.

1. A piezoelectric polymer material comprising a helical chiral polymerhaving a weight average molecular weight of from 50,000 to 1,000,000 andoptical activity, the piezoelectric polymer material having:crystallinity as obtained by a DSC method of from 20% to 80%; atransmission haze with respect to visible light of 50% or less; and aproduct of the crystallinity and a standardized molecular orientationMORc, which is measured with a microwave transmission-type molecularorientation meter at a reference thickness of 50 μm, of from 40 to 700.2. The piezoelectric polymer material according to claim 1, wherein theMORc is from 2.0 to 15.0.
 3. The piezoelectric polymer materialaccording to claim 1, wherein the transmission haze with respect tovisible light is from 0.05% to 30%, and the MORc is from 6.0 to 10.0. 4.The piezoelectric polymer material according to claim 1, wherein apiezoelectric constant d₁₄ measured by a displacement method at 25° C.is 1 pm/V or more.
 5. The piezoelectric polymer material according toclaim 1, wherein the helical chiral polymer is a polylactic acid-basedpolymer having a main chain containing a repeating unit represented bythe following Formula (1):


6. The piezoelectric polymer material according to claim 1, wherein thehelical chiral polymer has an optical purity of 95.00% ee or more. 7.The piezoelectric polymer material according to claim 5, furthercomprising polyvinylidene fluoride, wherein a content of thepolyvinylidene fluoride is from more than 0 mass % to 5 mass % withrespect to the total mass of the polylactic acid-based polymer; and apiezoelectric constant d₁₄ measured by a resonance method at 25° C. is10 pC/N or more.
 8. The piezoelectric polymer material according toclaim 7, wherein the content of the polyvinylidene fluoride is from 0.01mass % to 5 mass % with respect to the total mass of the polylacticacid-based polymer.
 9. The piezoelectric polymer material according toclaim 7, wherein a weight average molecular weight of the polyvinylidenefluoride is from 3,000 to 800,000.
 10. The piezoelectric polymermaterial according to claim 1, comprising from 0.01 to 1.0 part byweight of a crystal nucleating agent with respect to 100 parts by weightof the helical chiral polymer contained in the piezoelectric polymermaterial.
 11. The piezoelectric polymer material according to claim 10,wherein the crystal nucleating agent is at least one compound selectedfrom the group consisting of zinc phenylsulfonate, melaminepolyphosphate, melamine cyanurate, zinc phenylphosphonate, calciumphenylphosphonate, magnesium phenylphosphonate, talc and clay.
 12. Thepiezoelectric polymer material according to claim 1, wherein an area ofa principal plane is 5 mm² or more.
 13. A method for producing thepiezoelectric polymer material according to claim 1, the methodcomprising: obtaining a preliminarily crystallized sheet by heating asheet that is in an amorphous state and contains a helical chiralpolymer; and stretching the preliminarily crystallized sheet mainly in auniaxial direction.
 14. The method for producing the piezoelectricpolymer material according to claim 13, wherein in the obtaining of thepreliminarily crystallized sheet, the sheet in an amorphous state isheated to have a crystallinity of from 10% to 70% at a temperature Trepresented by the following expression:Tg≦T≦Tg+40° C. wherein Tg represents the glass transformationtemperature of the helical chiral polymer material.
 15. The method forproducing the piezoelectric polymer material according to claim 13,wherein in the obtaining of the preliminarily crystallized sheet, thesheet in an amorphous state comprises polylactic acid as the helicalchiral polymer and is heated at from 60° C. to 170° C. for from 5seconds to 60 minutes.
 16. The method for producing the piezoelectricpolymer material according to claim 13, wherein an annealing treatmentis performed after the stretching.
 17. A method for producing thepiezoelectric polymer material according to claim 1, the methodcomprising: stretching a sheet that contains a helical chiral polymermainly in a uniaxial direction; and performing a hydrolysis treatmentafter the stretching.
 18. A piezoelectric polymer material comprising apolylactic acid-based polymer and polyvinylidene fluoride, wherein acontent of the polyvinylidene fluoride is from more than 0 mass % to 5mass % with respect to the total mass of the polylactic acid-basedpolymer, and wherein a piezoelectric constant d₁₄ measured by aresonance method at 25° C. is 10 pC/N or more.
 19. The piezoelectricpolymer material according to claim 18, wherein the content of thepolyvinylidene fluoride is from 0.01 mass % to 5 mass % with respect tothe total mass of the polylactic acid-based polymer.